JPH0267549A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To execute development processing while a slit-shaped processing path is efficiently controlled in temp. by executing processing in the slit processing path and circulating a temp. control medium in the slit-shaped water path disposed along the slit processing path. CONSTITUTION:The processing of the silver halide photosensitive material S by the processing method including developing, desilvering, washing and/or stabilizing stages is executed in the slit-shaped processing path 15 and the temp. control medium is circulated in the slit-shape water path disposed along the processing path 15 at the time of executing the above-mentioned processing. The slit-shaped processing path 15 signifies that the section of the passage in a processing tank adapted to allow the passage of the photosensitive material S has a so-called slit shape of a small thickness with respect to the transverse width the transverse direction of the photosensitive material when the above- mentioned passage is cut perpendicular to the progressing direction of the photosensitive material S. The excellent temp. control is possible in this way even if a small-sized pump and a small-sized heater are used. The size and weight of the entire device are reduced.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to so-called slit development, in which silver halide photosensitive materials such as black and white films, black and white papers, color films, and color papers are processed in a slit-shaped processing path. This relates to a processing method.

[Conventional technology]

Generally, silver halide photosensitive materials are developed by passing them through rectangular parallelepiped processing tanks one after another containing processing solutions such as a developer, a bleaching solution, a fixing solution, and a stabilizing solution.

At this time, in order to obtain an even and uniform finishing performance, the photosensitive material is processed by immersing it in a large amount of processing solution, but if a large amount of processing solution is stored in the processing tank, the halogen When the amount of silver photosensitive material is small, the components in the processing solution may deteriorate due to air oxidation or carbon dioxide absorption, or the pH of the processing solution may decrease, which causes fluctuations in the performance of the photosensitive material after processing. It had become. As an effective means to solve these problems, there is a known slit development processing method that uses a slit-shaped processing tank to minimize the contact of the processing solution with air and process with the minimum necessary amount of solution. There is.

Normally, development processing is carried out under strict temperature control in order to obtain a uniform finish, and the means to do so is to heat each processing tank to a constant temperature and maintain the temperature of the processing solution inside at a constant level. Specific methods include a method using hot water, a method using a heater, and a method of circulating hot water.

On the other hand, even in slit development processing, in order to enable rapid and uniform development processing, it was necessary to maintain the processing path at a temperature suitable for each processing.

As a device used for slit development processing, JP-A-63-
No. 131138, etc., all of which have a device in which temperature-adjusted water is introduced into a space provided on one side of the processing channel to adjust the temperature of the processing liquid inside the processing channel to a desired temperature. being done.

However, this method requires a large amount of water to fill the entire space between the treatment channels with temperature-controlled water, so it takes a long time to reach the appropriate temperature, and it is difficult to circulate using a pump. However, a large pump is required, and the curved processing paths are in a bay, resulting in poor circulation, and even if a stirring device is provided, it is difficult to uniformly control the temperature. As a means of solving this problem, a method of installing temperature-controlled water outlets in several places was devised, but the overall size of the device became large, and this did not meet the purpose of the slit developing method, which aimed at compactness and rapid processing. .

Therefore, it has been desired to develop a method for controlling the temperature of the slit processing path, which enables miniaturization, speeding up, and uniform temperature control in the slit development processing.

[Problem to be solved by the invention]

Therefore, in the present invention, when performing slit development processing,
It is an object of the present invention to provide a method for processing a silver halide photosensitive material in which development processing is performed while efficiently controlling the temperature of a slit processing path.

[Means to solve the problem]

The present invention was completed based on the knowledge that the above-mentioned problems can be efficiently solved by providing a specific temperature-adjusting slit-shaped waterway in contact with the slit-shaped processing path when performing slit development processing.

That is, in the present invention, when a silver halide photosensitive material is processed by a processing method including development, desilvering, water washing, and/or stabilization steps, the above processing is carried out in a slit-shaped processing path, and the processing is carried out along the slit processing path. The present invention provides a method for processing a silver halide photosensitive material, which is characterized by circulating a temperature regulating medium in a slit-shaped waterway arranged in a slit-shaped waterway.

The slit-shaped processing path used in the development process of the present invention is defined as the width of the cross section (in the width direction of the photosensitive material) when the path in the processing tank through which the photosensitive material passes is cut at right angles to the traveling direction of the photosensitive material. This means that it has a so-called slit shape with a thinner thickness than the other one. Note that the cross section of the slit shape may be rectangular or oval.

The shape of a processing tank having such a slit processing path is defined as follows.

V/L≦20, particularly preferably V/L≦1O. Here, V is the volume (c[II) of the processing liquid accommodated in the processing path, and L
is the length (cm) of the central path (processing path) of the photosensitive material from the artificial side liquid level of the photosensitive material to the outlet side liquid level of the processing tank.

Therefore, the slit processing path is characterized by a small amount of liquid accommodated relative to the length of the path. In other words, since the amount of liquid is small, the liquid in the processing path (processing tank) can be replaced quickly by replenishing the processing liquid.In other words, the residence time of the liquid in the processing tank can be shortened, and fatigue of the processing liquid over time can be avoided. Can be done. However, for practical purposes, the lower limit of V/L is preferably 0.1, particularly preferably 0.5.

In the processing path, specifically, V is 10,000 to 100c.
af is preferred, particularly preferably 5000 to 200ca
f, most preferably 1000-300cI11.

Further, L is preferably 300 to 10 cm, particularly preferably 200 to 20 cm, and most preferably 100 to 30 cm.

When processing is performed using a slit processing path, the liquid volume V (CI
It is preferable to use a processing tank in which the liquid area S (crI) (hereinafter referred to as opening area) that comes into contact with air is small compared to 11). Specifically, it is preferable that V and S have the following relationship.

S/V≦0.05, particularly preferably S/V≦0.01. In other words, S/
The smaller V is, the less likely it is to be oxidized by air, and the less evaporation of the liquid, the more the liquid can be stored stably for a long period of time.

However, practically, the lower limit is preferably 0.0005, particularly preferably 0.001.

In the above regulations, the thickness of the slit-shaped processing path is 1 to 50
Preferably m[Il, especially 3 to 30[0111
is preferred.

In addition, the conveyance speed of the photosensitive material in the slit processing path is 10 cm.
The speed range is preferably from 20 to 200 cm/min, and most preferably from 20 to 120 cm/min to obtain an even and uniform finishing performance.

When processing is performed in the above slit processing path, changes in the processing solution in the processing tank occur, specifically, oxidation of the developing agent and preservative, decrease in pH due to absorption of carbon dioxide in the air, and concentration due to evaporation of water. , various decompositions of treated liquid components due to long-term residence in the tank,
This has the great advantage of eliminating factors of variation in conventional processing, such as mutual unfavorable reactions. Therefore, even in slow processing where the amount of photosensitive material to be processed is small, it is possible to perform processing in which the finishing performance of the photosensitive material, such as gradation, fog, and sensitivity, is less likely to fluctuate. Furthermore, it is easy to make the processing apparatus more compact, and since the opening area is small, the complexity of using a conventional floating lid can be avoided.

In the present invention, the slit-shaped processing path includes one in which at least a portion of the portion other than the roller for conveying the photosensitive material is slit-shaped, and the length of the slit-shaped processing path between the conveyance roller and the roller is 5 cm or more, preferably 1
It is better to have a diameter of 0 cm or more.

Note that a flexible member (such as nylon or polyester) can be provided on the inner wall of the slit-shaped processing path so as to protrude inward.

In the present invention, when performing slit development, it is further preferable to use a processing tank in which the ratio of the liquid surface area to the liquid volume is small, and in this processing tank, the cross-sectional area of the processing liquid path is approximately the same as the surface area of the liquid surface part. This is preferred, and so-called thin layer development is preferred.

Furthermore, the liquid flow path in the main part of the developing tank and the withdrawal path of the photosensitive material are almost parallel, and in the main part, the liquid flow path in the main part of the photosensitive material is perpendicular to the emulsion layer and the support layer (in the thickness direction).
The length is within 200 times the thickness of the photosensitive material, and more preferably 2 to 20 times the thickness of the photosensitive material.
Preferably, the processing liquid path is 100 times larger, particularly 5 to 50 times larger. In this case, the gap between the processing tank and the photosensitive material in the thickness direction is 0.3 to 30 mm, preferably 0.5 to 10 mm.
mm, particularly preferably 0.5 to 3 mm.

In the present invention, a developing solution, a bleaching solution,
It is filled with a bleach-fix solution, a fixing solution, washing water, a stabilizing solution, etc., and the exposed silver halide photosensitive material is passed through them for development processing. Incidentally, examples of the developer include a black and white developer and a color developer (including a reversal color developer). Specifically, the slit developing method of the present invention includes the following steps.

(1) Development - Bleach fixing - Washing - Drying (2) Development - Bleach fixing - Stabilization - Drying (3) Development - Bleach fixing - Washing - Drying (4) Development - Bleach fixing - Stabilization - Drying (5) ) Development - bleach fixing - washing - stabilization - drying [6] Development - bleach fixing - washing - stabilization - drying (7) Black and white development - washing - reversal - color development - washing - bleaching - washing - stabilization - stabilization Water washing can be provided between development and bleaching in the above processing steps. Furthermore, steps such as stopping, adjusting, and neutralizing can be provided as appropriate.

Incidentally, in the case of a black-and-white photographic material, the bleaching step and the stabilizing step can be omitted in the above (3) to (5).

In the above-mentioned slit developing method, it is preferable that the processing liquid is divided and supplied into the slit processing path along the traveling direction of the silver halide photosensitive material within the processing path.

Here, at least one of the above-mentioned processing liquids can be mentioned as the processing liquid to be supplied in parts, but all the processing liquids can also be supplied in parts. Furthermore, divided supply means, for example, when supplying a developer, the developer is supplied to at least two locations along the traveling direction of the silver halide photosensitive material within the slit processing path containing the developer, preferably two to two locations. This means that it is divided into 5 portions and supplied.

When the developer is supplied in parts, a supply port is provided at a position where the photosensitive material enters the developer in the developer tank, and 30 to 70%, preferably 40 to 60%, of the total developer replenishment amount is supplied from the supply port.
%, and the remainder is divided according to the number of supply ports, and is preferably supplied from a supply port provided downstream of the position where the photosensitive material enters the developer.

On the other hand, bleach solution, bleach-fix solution, fixing solution, washing water, stabilizing solution, etc. differ from the order in which the developer is supplied.
30 to 70%, preferably 40 to 60%, of the replenishment amount of the processing solution is supplied from a supply port provided in a countercurrent direction to the conveyance direction of the photosensitive material, that is, at a position where the photosensitive material exits from the processing solution, and the remaining amount is It is preferable that the photosensitive material be divided into parts according to the number of supply ports and supplied from the supply ports provided upstream of the position where the photosensitive material comes out.

The above-mentioned slit development may be carried out using, for example, an automatic developing machine in which all processing paths for introducing processing solutions (developing solution, bleaching solution, fixing solution, washing water, etc.) shown in Fig. 1 are formed as slit-shaped processing channels. Can be done. Further, in carrying out the slit treatment, a roller withdrawal method as shown in FIGS. 2 and 3 may be used as the treatment path.

The present invention is characterized in that, in such slit development processing, a temperature regulating waterway is provided in contact with the processing path.

The temperature regulating waterway in the present invention is preferably a flat waterway that is in contact with the slit processing path and runs alongside the slit processing path from the photosensitive material inlet portion to the exit portion.

In order to circulate the temperature regulating medium, the water channel is connected from the photosensitive material exit section of the slit processing path to the photosensitive material entry section by a bypass passing outside the apparatus, and a temperature regulating heater and a circulating medium are connected to the bypass section. It is preferable that the temperature regulating medium is circulated in the same direction as the traveling direction of the photosensitive material from the entrance side of the slit processing path through a part of the heater, but in some cases it may be circulated in the opposite direction. can. Examples of the temperature regulating medium include water, saline, and mirabilite water, and water is preferably used.

It is preferable that no space exists between the slit treatment channel and the water channel, and it is particularly preferable that they are in close contact with each other. The processing channel and the water channel are usually made of 0.2-5 mm stainless steel material, which allows for good heat transfer and uniform stainless steel temperature control. However, since irregularities may exist on the outer wall of the processing path, etc. due to roller withdrawal, some gaps may be partially provided in such cases.

The waterway is usually 1 to 50 mm, preferably 5 to 20 mm.
It is preferably flattened in the same direction as the slit processing path. In order to uniformly control the temperature of the slit processing channel, the width of the channel is preferably the same as the width of the slit processing channel, but as long as sufficient temperature regulation is obtained, the width of the channel should be the same as the width of the slit processing channel. It can be narrower or wider than the width.

Furthermore, the present invention also includes a system in which the slit processing path and the water channel are integrally formed, that is, the temperature control medium and the processing liquid may be separated by providing a partition plate in the slit processing path.

In addition, the water channel may be located below or above the slit treatment channel, or may be located on both sides thereof, or the top and bottom may be partially reversed.

By using such a temperature regulating waterway, the amount of temperature regulating medium can be reduced to an extremely small amount. Conventional temperature regulating water equipment for slit processing requires the use of temperature regulating water of approximately 40 to 90 f, and is large (601/min,
Even if you use a pump of
It took about 120 minutes, and it also took about 50 minutes using the IKW heater to raise the temperature of the temperature-adjusted water to a predetermined temperature.

In the temperature control method of the present invention, it is usually sufficient to use 41 temperature control media, so a small pump (201/min) is required.
Even when using a small heater (0.5 KW), the temperature regulating medium will be circulated approximately 5 times/min. Overall, it is possible to achieve very good temperature regulation.

Furthermore, there is no need for a blow-off port or a stirring device for the temperature-adjusting medium, which are necessary in conventional apparatuses, and the entire automatic developing machine can be made extremely compact.

In the slit development processing method, since the amount of processing solution used is small, when the photosensitive material is introduced into the processing path for development processing, the temperature of the developing solution near the entrance of the processing path decreases significantly. Conventional temperature control devices cannot effectively cope with such a temperature drop because the amount of temperature control water circulated is low, resulting in drawbacks such as uneven development. However, in the temperature control method of the present invention, the temperature control medium heated by a heater warms the processing path near the processing path where the photosensitive material is introduced, and the number of circulation is large, so that the processing due to the introduction of the photosensitive material The drop in temperature of the solution is extremely small, and stable development processing is possible.

However, if each treatment liquid requires a different optimum treatment temperature, desired temperature adjustment becomes possible by arranging a heater near each treatment tank.

Next, the processing liquid used in the processing method of the present invention will be explained.

Development Treatment In the present invention, a color developer or a black and white developer is used as the developer.

Among these, the color developing solution is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 3-methyl-4
-Amino-N.

N-diethylaniline, 3-methyl-4-amino N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4 -amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, various substances such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, and triethylenediamine (1,4-diazabicyclo[22,2]octane) may be added. Preservatives, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, 1 - Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity-imparting agents, various calcinants such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, e.g. Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N, N, N'N
'-tetramethylenephosphonic acid, ethylene glycol (
(0-hydroxyphenylacetic acid) and their salts are representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as ■-phenyl-3-pyrazolidone, or amine phenols such as N-methyl-p-aminophenol are used alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12.

Bleaching and/or fixing treatment (desilvering treatment) After color development, a bleaching treatment is usually performed. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, processing in two consecutive bleach-fixing baths, or carrying out a fixing process after a bleach-fixing process can be carried out as desired depending on the purpose.

As a bleaching agent, for example, iron (■), Kobal) (III
), compounds of polyvalent metals such as chromium (■), copper (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I [I] or cobal) (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1, Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (II) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (DI) complex salts, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (I[[) complex salts is usually 5.5 to 8, but in order to speed up the processing, it may be processed at an even lower pH of 9H. You can also do it.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Useful bleach accelerators include those specifically described in U.S. Pat.
No. 893.858, West German Patent No. 1.290.812,
Compounds having a mercapto group or disulfide bond described in JP-A-53-95630, Research Disclosure +-N (No. 117,129 (July 1978), etc.; Tiapridine described in JP-A-50-140129) Derivatives: Thiourea derivatives described in U.S. Patent No. 3,706,561; Iodide salts described in JP-A-58-16235; Polyoxyethylene compounds described in West German Patent No. 2,748,430: Examples include polyamine compounds described in Japanese Patent Publication No. 45-8836; bromide ions, etc. Among them, compounds having a mercapto group or a disulfide group are preferred because they have a large promoting effect, and are particularly preferred as described in US Patent No. 3.
No. 893.858, West German Patent No. 1.290.812,
Compounds described in JP-A-53-95630 are preferred.

Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for Preservatives for bleach-fix solutions include sulfites and bisulfites.

Alternatively, carbonyl bisulfite adducts are preferred.

Water Washing and/or Stabilization Process After the above desilvering process, a water washing and/or stabilization process is generally performed. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range.

Among these, the relationship between the number of flushing tanks and athlete's foot in the multistage countercurrent method is described in the Journal of the 5o
City of Motion Picture
eand Te1evision Engineers
Volume 64, P, 248-253 (May 1955
It can be obtained by the method described in the monthly issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
Calcium ions described in JP-A No. 62-88838,
A method of reducing magnesium ions can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi , Sanitation technology complete volume "Microbial sterilization, sterilization, and anti-mold technology"
It is also possible to use the disinfectants described in "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japanese Society of Antibacterial and Antifungal Agents.

The pH of the washing water used is 4-9, preferably 5.
-8. Washing water temperature and washing time also depend on the characteristics of the photosensitive material.
Although various settings can be made depending on the purpose, generally the temperature is 15-45°C for 20 seconds-10 minutes, preferably 25-40°C for 30 seconds-5
A range of minutes is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-14
834 and 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

Photosensitive materials processed by the method of the present invention include color photosensitive materials as well as black and white photosensitive materials. For example, color paper
In addition to color reversal paper, color negative film for photography, color reversal film, negative or positive film for movies, and direct positive color photosensitive materials, examples include X-ray film, photosensitive materials for printing, microfilm, and black and white film for photography. can.

Any known silver halide emulsion for light-sensitive materials can be used. Silver chlorobromide emulsion (silver chloride content of 90 mol % or more is preferred for rapid processing) is used for color printing photosensitive materials, and silver iodobromide emulsion (containing silver iodide) is used for color photosensitive materials for photography. The amount is preferably 2 to 15 mol%). In particular, in slit development, it is preferable to use a silver chloride/silver sensitive photosensitive material because no bromide ions are released into the developer, and development unevenness due to non-uniform dispersion of bromide ions is less likely to occur. Moreover, since the developing speed is fast, the length of the slit processing path can be shortened, the processing apparatus can be easily made compact, and non-uniform distribution of the concentration of the processing liquid can be eliminated, which is preferable. Silver halide grains are spherical, cubic, octahedral, rhombic dodecahedral, tetradecahedral, etc., and tabular (preferably aspect ratio 5 to 20) are used for high-sensitivity photosensitive materials.
) is preferred. These particles may have a uniform phase or may have a multilayer structure. Further, the particles may be surface latent image type particles or internal latent image type particles.

The particle size distribution may be polydisperse or monodisperse (preferably standard deviation/average particle size≦15%), but the latter is preferred. These silver halide grains may be used alone or in combination depending on the purpose.

The above photographic emulsion is a research disclosure (RD)
) vol, 176 1temNc17643 (1°■,■) (December 1978).

Furthermore, emulsions that have been subjected to physical ripening, chemical ripening, and spectral sensitization can usually be used. Additives used in such processes are listed in Research Disclosure Vol. 176, Nα17643 (December 1978) and Research Disclosure Vol.
It is described in Volume 87, Nα18716 (November 1979), and the relevant parts are summarized in the table below.

Furthermore, known photographic additives that can be used are also listed in the above two Research Disclosures, and the locations listed are shown in the table below.

Additive type 1 Chemical sensitizer 2 Sensitivity enhancer 5 Brightener 7 Coupler 8 Organic solvent 9 Light absorber, filter dye Ultraviolet absorber Stain inhibitor Dye Image stabilizer Hardener Binder Plasticizer, lubricant RD17643 RD1871623 page
Page 648 Right column Same as above Same as above Page 24 Page 25 Page 25 Pages 25-26 Same as above Page 25 Right column Page 25 Page 26 Page 26 Page 27 Same as above Same as above Same as above Page 649 Right column - Page 650 Left column Same as above 650 Page Left - Right column Same as above 651 Page left column Same as above page 650 right column Color photosensitive materials can contain various color couplers, specific examples of which are disclosed in the patents described in Research Disclosure (RD) Nα17643, ■-〇~G mentioned above. has been disclosed.

As dye-forming couplers, couplers that provide the three subtractive primary colors (i.e., yellow, magenta, and cyan) in color development are important, and diffusion-resistant, 4-equivalent or 2-equivalent couplers are important.
As specific examples of equivalent couplers, in addition to the couplers described in the above-mentioned patents described in RD17643, ■-○ and section D, the following can be preferably used.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used include hydrophobic 5-pyrazolone and pyrazoloazole couplers that have a ballast group. As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye.

Cyan couplers that can be used include hydrophobic, diffusion-resistant naphthol and phenolic couplers.
Preferably, a two-equivalent naphthol coupler of oxygen atom separation type is mentioned as a representative example. Additionally, couplers that form cyan dyes that are stable to humidity and temperature are preferably used, exemplified by U.S. Pat.
2.002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus; 2.5-diacylamino-substituted phenolic coupler, having a 7-enylureido group at the 2-position and a 5- These include phenolic couplers having an acylamino group at the acylamino positions, and 5-amidenaphthol cyan couplers described in European Patent No. 161.626A.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
Specific examples of magenta couplers are described in US Pat. No. 4,366,237, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3.451.82.
It is written in No. 0, etc. Specific examples of polymerized magenta couplers are described in U.S. Pat. No. 4,367,282 and elsewhere.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD17643,
The patent couplers listed in Sections .-F. are useful.

In the light-sensitive material processed in the present invention, a coupler that releases a nucleating agent or a development accelerator or a precursor thereof in an imagewise manner during development can be used. Specific examples of such compounds are given in British Patent No. 2.097.140;
．． No. 131.188. In addition, DIR redox compound-releasing couplers described in JP-A-60-185950 and the like, couplers that release dyes that recover color after separation as described in European Patent No. 173.302A, and the like can be used.

〔Effect of the invention〕

According to the present invention, it has become possible to control the temperature of the processing solution in slit development processing with a very small amount of temperature control medium, and uniform development processing has become possible. Furthermore, the entire slit processing apparatus could be made significantly smaller and lighter.

Next, the present invention will be explained with reference to examples.

〔Example〕

Example 1 Slit type automatic developing machine 1 shown in Fig. 1 (cross-sectional view shown)
The exposed color paper was processed using FIG. 2 is a detailed sectional view of section 21 (color developing section) in FIG. 1. Here, as a transportation method for photosensitive materials, the width is 89mm,
A polyester endless belt with a thickness of 0.18 n+m was used. A photosensitive material having a width of 82.5 mm to be processed was attached with a bonding tape and held on a belt for development processing.

In FIG. 2, a lid 8 with a comb-shaped upper lid 6 hanging thereon is placed in a housing 4 in a developing processing tank P1 to form a narrow (slit-like) processing passage 15.

A handle 10 is provided on the lid 8. The upper lid 6 has a plurality of vinyl chloride upper lid members 12 having a rectangular cross section arranged almost vertically, and a silver halide photosensitive material (
A feed reel 16 of S) is arranged.

Inside the processing housing 4, a tank wall material 14 that is combined with the upper lid material 12 to form a processing path 15 (width 3+n+n) is arranged. Therefore, the upper lid material 12 and the tank wall material 14 are
A continuous wave-shaped processing path 15 is formed, and photosensitive material feeding reels 16 are arranged at the upper and lower bends of the processing path 15, respectively.

In FIG. 2, three photosensitive material feeding reels 16 are provided at the top and four at the bottom.

An overflow hole 20 and a replenishment port 22 are provided at the slit-shaped inlet and outlet portions of the processing path 15, and the level of the developer in the processing path 15 is never higher than the overflow hole 20.22. Furthermore, above the inlet and outlet portions of the processing path 15, a photosensitive material supply reel 24 and a photosensitive material take-out reel 26 are arranged. In order to form a temperature regulating channel 55, a temperature regulating channel wall material 54 was further provided outside (lower side in the figure) of the tank wall material 14. Inlet 5 of temperature control waterway 55
From 6, a heater H for heating the medium and a pump P for feeding the liquid are used to flow the medium at the set liquid temperature, and the temperature control waterway 5
The medium discharged to the outlet of 5 is again pumped P and heater H.
circulate through.

In the above configuration, a color developing solution (D) was placed in the processing path 15. Then, the photosensitive material S is transferred to the photosensitive material supply reel 24.
The photosensitive material is supplied to the processing path 15 via a plurality of photosensitive material feed reels 16, is developed, and is taken out by a photosensitive material take-out reel 26. The endless belt has the endless belt path shown in Figure 1.
After passing through the winding section Tu provided outside the apparatus, it was led back into the slit processing path.

Pour 3.5 liters of hot water for temperature adjustment into the temperature adjustment waterway, and
Heater (0,
9KW).

Next, Nos. 571 to 57 of Japanese Unexamined Patent Publication No. 63-70857
After exposure, the seven-layer color paper described in Example 2 on page 5 was fixed to an endless belt with a joining tape, and subjected to the color treatment in Example 2 described on pages 566 to 571 of the same publication. Note that deionized washing water (B) was used for washing.

Example 2 An exposed silver halide photosensitive material was processed using a slit-type automatic processor shown in FIG. 3 (a cross-sectional view is shown). In FIG. 3, the developing tank 2 includes a processing housing 4.
A lid 8 with a comb-shaped upper lid 6 suspended therein was placed to form a narrow (slit-like) processing passage 15. Handle 1 on lid 8
0 is set. The upper lid 6 has a plurality of vinyl chloride upper lid members 12 each having a rectangular cross section arranged substantially vertically, and a feed reel 16 of silver halide photosensitive material (S) is arranged at the joint portion of the upper and lower ends of these upper lid members 12 .

Inside the processing housing 4, a tank wall material 14 is arranged which forms a processing path 15 (width 3 mm) in combination with the upper cover material 12. Therefore, the upper lid material 12 and the tank wall material 14 form a continuous wave-shaped processing path 15, and photosensitive material feeding reels 16 are arranged at the upper and lower bends of the processing path 15, respectively.

In FIG. 3, two photosensitive material feeding reels 16 are provided at the top and three at the bottom.

An over hole 22 and a replenishment port 20 are provided at the slit-shaped artificial part and the outlet part of the processing path 15, so that the developer level in the processing path 15 is never higher than the overflow hole 22. Further, above the input section and the exit section of the processing path 15, a photosensitive material supply reel 24 and a photosensitive material take-out reel 2 are provided.
6 is placed. A temperature regulating medium path wall material 54 was provided on the outside (lower side in the figure) of the tank wall material 14 at the height where the temperature regulating medium path 55 was formed. Population 5 of temperature regulating medium path 55
From 6, a medium at a set liquid temperature is made to flow in using a heater H for heating the medium and a pump P for sending the liquid, and is then flowed out to the outlet of the temperature adjusting medium path 55, and this medium is passed through the pump P and the heater H again. and circulate.

In the above configuration, a color developer (D) is provided in the processing path 15.
, bleach-fix solution (BF), and washing water (W) were added. Then, the photosensitive material S is supplied to the processing path 15 via the photosensitive material supply reel 24, is developed while being conveyed by a plurality of photosensitive material feed reels 16, and is transferred to the photosensitive material take-out reel 2.
6.

Pour 3 Il of hot water for temperature control into the temperature control waterway, circulate it with a pump of 61/min, and heat the heater (0.9K) to 35.2℃.
W).

Next, JP-A No. 63-108339 (Japanese Patent Application No. 61-25)
After exposing the color paper described in Example 2 on pages 337 to 341 of the Japanese Patent No. 4878), it was treated by the slit phenomenon treatment method shown in FIG. 3 using the following treatment liquid. The withdrawal method followed the method of Example 1.

(Color developer) Sodium chloride triethanolamine mother solution 00d g g Replenisher 80〇-g Water mother solution and replenisher same 600ml! Potassium carbonate 6 g 6 g Sodium sulfite 0.1 g 0.2 g Add potassium bromide water (bleach-fix solution) 0.02 g 1 β 10,05 10.65 Sodium sulfite 16 g Glacial acetic acid
Add 7g water
11P8 5
．． 5 (Washing water) Deionized water (conductivity 3 μs/am) The replenishment amount is:
8.25 Cm width per meter, color developer 1
0mf bleach-fix solution 10mj! Washing water 30mj! And so.

The capacities of the treatment tanks in Examples 1 and 2 are shown in Table 1.

No. table This was used as a comparative example.

The results obtained in Example 1, Example 2, and Comparative Example are shown in the table below.

*Only P1 is slit type Processing times and temperatures are as listed in the table below.

1) Slit tank 2) Normal processing tank The processing time in the table is the time from contact with the liquid until contact with the liquid of the next step.

In Embodiment 1, the temperature control waterway wall material 54 is not provided, and hot water is supplied inside the phenomenon housing 4.As is clear from the barley, even if a small pump and a small heater are used in the embodiment, excellent temperature is maintained. Adjustment became possible, and an excellent effect was achieved in making the entire device smaller and lighter.

[Brief explanation of the drawing]

Fig. 1 is a sectional view of the photo developing machine used in the present invention, Fig. 2 is a detailed sectional view of the P1 section in Fig. 1, and Fig. 3 is a modified example of the photo developing machine used in the present invention. FIG. In the figure, 15... Processing channel, 54... Wall material for temperature regulating channel, 55... Temperature regulating channel, 56... Temperature regulating medium inlet/outlet, S... Photosensitive material fixed on belt, P.
... Pump, H... Indicates a heater.

Claims (1)

[Claims] When processing a silver halide photosensitive material using a processing method including development, desilvering, water washing, and/or stabilization steps, the above processing is carried out in a slit-shaped processing path, and a slit-shaped A method for processing a silver halide photosensitive material, which comprises circulating a temperature regulating medium in a water channel.