JPH04151656A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an image having satisfactory photographic performance by a processing with an automatic processing machine fitted with a conveying belt, to prevent deterioration even after use over a long period of time and to ensure superior durability by using polyvinylidene fluoride resin fibers or polyethlene fibers having ultrahigh strength as a core material embedded in the base of the conveying belt and specifying the replenishing amt. of a color developing soln. CONSTITUTION:Plyvinylidene fluoride resin fibers or polyethylene fibers having ultrahigh strength are used as a core material 17 embedded in the base 11 of a conveying belt 1 and the replenishing amt. of a color developing soln. is regulated to <=700ml per 1m<2> of a silver halide color photographic sensitive material. In this case, any substance affecting the developing performance of the color developing soln. is not eluted and photographic performance is not degraded. Even when the core material 17 is not completely embedded, degradation is hardly caused. Images having satisfactory photographic performance are constantly obtd. over a long period of time by continuous processing under low replenishment with an automatic processing machine using a belt conveying system.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for processing silver halide color photographic materials using a belt conveyance type automatic developing machine.

<Prior art> Silver halide color photographic light-sensitive materials (hereinafter sometimes referred to as light-sensitive materials or photosensitive materials) undergo color development, desilvering,
It is processed through processes such as washing with water and stabilization.

A color developer is used for color development, a bleach solution, a bleach-fix solution, or a fixer is used for desilvering treatment, tap water or ion exchange water is used for washing, and a stabilization method is used for stabilization treatment.

The temperature of each processing solution is usually adjusted to 30 to 40°C, and the photosensitive material is immersed in these processing solutions to be processed.

Among the above processing steps, the basic ones are a color development step and a desilvering step.

In the color development step, exposed silver halide is reduced by a color developing agent to yield silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image.

In addition, in the desilvering step that follows this color development step, the silver produced in the color development step is oxidized by the action of a bleaching agent, which is an oxidizing agent, and then dissolved by a fixing agent, which is a complex ion forming agent for silver ions. Only a dye image is formed.

The above-mentioned desilvering step includes a method in which the bleaching step and the fixing step are performed in the same bath, a method in which the steps are performed in separate baths, and a method in which the bleaching step and the bleach-fixing step are performed in separate baths. Moreover, in this case, each bath may be multi-tank.

In addition to the above-mentioned basic steps, various auxiliary steps are performed for the purpose of maintaining the photographic and physical quality of the dye image or improving its shelf life. Such a step is carried out using, for example, a hardening bath, a stopping bath, a stabilizing bath, a washing bath, and the like.

Such a process is generally performed using an automatic development method, and the photosensitive material is processed by sequentially conveying it between processing tanks filled with each processing solution.

By the way, among such automatic developing machines (hereinafter sometimes abbreviated as automatic developing machines), there is a type in which a photosensitive material is conveyed by driving force using an endless belt.

In particular, such a belt conveyance type automatic processing machine has a large number of processing steps and is used for processing color negative films and the like that have a narrow and long shape.

For example, if an automatic processor with a hanging development method is used to process such photosensitive materials, the equipment will be large, resulting in high costs, restrictions on installation location, and shortening of crossover time. This may result in longer processing times,
This is because belt conveyance is more advantageous because of its firepower.

An example of an automatic processor using such a belt conveyance method is the one disclosed in Japanese Utility Model Application Publication No. 191258/1983. In this system, a league is attached to the leading edge of the film, and by engaging this leader with an endless belt, conveying force is applied to the film.This allows the film to pass through each processing tank, and then the film is passed through a dryer. are being accumulated.

Some of these film conveyance belts are made of materials such as polypropylene, but in order to achieve both strength and cost, the belt base is made of urethane resin, and aramid fibers are embedded in this as a core material. things are used.

However, it has been found that when a belt having a core material of aramid fiber as described above is used for a long period of time, problems in photographic performance such as softening of tone occur.

Such problems are noticeable in processes that reduce the amount of replenishment of color developer, and have become more serious in recent years as low-replenishment processes have become mainstream for purposes such as resource saving and environmental conservation. do.

Furthermore, the above-mentioned deterioration in photographic performance becomes a particular problem in light-sensitive materials in which the amount of coated silver is small.

Furthermore, belts made of aramid fibers do not have sufficient strength (with long-term use, the belt may deteriorate, crack, or in the worst case, break, leading to an accident).

<Problems to be Solved by the Invention> An object of the present invention is to obtain images with good photographic performance in processing using an automatic developing machine equipped with a conveyor belt, and to avoid deterioration even after long-term use. An object of the present invention is to provide a method for processing a silver halide color photographic material using a conveyor belt having excellent durability.

Means for Solving the Problems> The above object is achieved by the present invention having the following configurations (1) and (2).

(1) The silver halide color photographic material is processed by an automatic developing machine having a processing tank filled with a processing solution containing at least a color developing solution, and a conveying belt provided in the processing tank for transporting the silver halide color photographic light-sensitive material. In the method of processing photographic light-sensitive materials, the core material embedded in the belt base of the conveying belt is made of ultra-high strength polyethylene fibers or polyvinylidene fluoride resin fibers, and the replenishment amount of the color developer is adjusted to halogen 1. A method for processing a silver halide color photographic material, characterized in that the amount of silver halide color photographic material is 700 ml or less per 1 m'' of the silver halide color photographic material.

(2) The method for processing a silver halide color photographic material according to (1) above, wherein the amount of coated silver in the silver halide color photographic material is 5 g/+'' or less.

<Function> With conventional conveyor belts that use aramid fibers as the core material, deterioration of photographic performance, which is thought to be caused by elution from the aramid fibers, occurs during long-term continuous processing with a reduced amount of color developer replenishment. arise.

This deterioration in photographic performance is mainly caused by a softening of the contrast.
The above-mentioned eluate is considered to be the organic solvent eluted into the color developing solution by the surfactant and the like, which are eluates from the sensitive material.

Furthermore, aramid fibers have the problem of belt deterioration, resulting in cracks in the belt after long-term use, or in the worst case, belt breakage.

This deterioration is caused by the fact that it is technically difficult to completely embed the core material in the belt base made of urethane resin, etc. in conveyor belts, and the existence of unembedded parts and joints. It is thought that this will occur.

However, in the present invention, since ultra-high strength polyethylene fibers or polyvinylidene fluoride resin fibers are used as the core material, there is no elution of substances that would inhibit the development performance of the color developer, and there is no deterioration of photographic performance.

Furthermore, even if there are parts of the core material in the present invention that are not completely embedded, there is almost no deterioration from such parts (and the conveyor belt has excellent durability).

<Specific configuration> Hereinafter, a specific configuration of the present invention will be explained in detail.

The method for processing a silver halide color photographic light-sensitive material of the present invention is carried out using an automatic processor equipped with a conveyor belt provided in a processing tank.

An example of the conveyance belt in this case is the one shown in FIG.

Such a conveyor belt is used as an endless belt by being suspended from a sprocket in a processing tank, and a portion thereof is shown in FIG.

Moreover, this product is mainly used for transporting films.

As shown in FIG. 1, the belt 1 has a narrow and thin belt base 11, and one side of this base 11 has a timing protrusion that fits into a square hole of a film league as described later. Certain trapezoidal protrusions 13 are provided at equal intervals. Further, on the other side, engaging protrusions 15 having a width larger than the width of the trapezoidal protrusions 13 are provided at equal intervals at positions corresponding to these trapezoidal protrusions 13.

Also, in FIG. 2a, I-I of the belt 1 in FIG.
A line (longitudinal) cross-sectional view is shown in FIG. 2b, and a shoreline cross-sectional view taken along the line (--) in FIG. 2a, respectively.

As shown in FIGS. 1 and 2, the belt 1
Now, two core members 1 are placed near both sides of the trapezoidal protrusion 13.
7 is in the longitudinal direction of the belt 1 and is embedded in the belt base 11.

Such a belt 1 is usually made of synthetic resin and is produced by integral molding.

In the present invention, the base of the conveyor belt as described above is not particularly limited as long as it is made of a material that has a certain degree of elasticity and does not adversely affect the processing liquid (specifically, it may be made of a hard urethane resin or an olefin-based material). Examples include thermoplastic elastomers such as elastomers, and among them, hard urethane resins are preferably used. Note that the hard urethane resin is selected from thermosetting urethane resins and thermoplastic urethane resins.

The width of such a belt base may be about 0.5 to 5 cm, and the thickness may be about 0.1 to ICDI.

The material of the trapezoidal protrusion 13 and the engagement protrusion 15 shown in FIGS. 1 and 2 may be the same as that of the belt base.

Further, the core material embedded in the belt base is formed from ultra-high strength polyethylene fibers or polyvinynodene fluoride resin fibers.

The reason for using such fibers is as follows.

■Do not dissolve substances that would inhibit the development performance of the color developer during long-term continuous processing.

(2) Properties such as strength can be maintained even in a color developing solution with a relatively high pH (about 9.5 to 11).

■It can maintain its function as a conveyor belt for a long time.

Ultra-high strength polyethylene fibers are obtained by stretching and orienting ultra-high molecular weight polyethylene.

Furthermore, from the viewpoint of the function as a conveying belt, specifically expressing the mechanical properties of ultra-high strength polyethylene fibers, it is desirable that the elongation at break is 7% or less. Also, the strength is 20
0kg/+oz” or more is desirable, and the elongation is at least 7
% or less, it is desirable to be able to maintain a strength of 2 kg/+nm'' or more.

The purpose of setting such a breaking elongation is to prevent conveyance defects due to positional deviations such as the pitch of the trapezoidal protrusions of the belt being deviated from the square holes of the leader due to elongation of the belt. Further, the strength as described above is provided in order to cope with tension support that is applied when a film jams.

Furthermore, when reinforcing the belt, it is preferable that the specific strength and specific elasticity are high.
00kg/a+m2, density is 1.1 or less, preferably 1
．． 06-0.94, elastic modulus 500 kg/ml112
Above, preferably 5200 to 1,3000 kg/wm
”, the crystallinity is preferably 70% or more, preferably 85% or more.

In addition, it is preferable that adhesiveness with the material of the belt base is sufficiently ensured, and the glabellar shear strength (ILSS) with respect to the material of the belt base, such as hard urethane resin, is 5.
0MPa (approximately 5kg/mm"), but ILSS
Higher values are preferable.

As the ultra-high strength polyethylene fiber, commercially available products can be used as they are, such as those with the trade names of Dynima 5K60 (manufactured by Toyobo Co., Ltd.), Tecmilon (manufactured by Mitsui Petrochemical Co., Ltd.), and Spectra (manufactured by Allied Corporation). , any of them can be preferably used.

The basic performance of such fibers is as follows. Two types of the above-mentioned commercially available products are shown below.

As evidenced by the above characteristic values, the ultra-high strength polyethylene fiber has sufficient strength as a core material and can be used as it is as a commercially available product.

Such fibers are commercially available in the form of long fibers (filaments) and are usually composited in a unidirectional arrangement, as shown in FIGS. 1 and 2.

In this case, the filaments are used in the form of multifilaments.

Since monofilament has a diameter of 100 to 1600 deniers for boat fishing, it is preferable to use 10 to 1600 filament yarns. For example, each core material 17 shown in FIG. 2b is made of 1170 filament yarns, and its diameter is 1
．． It is about 0±0.3 mm.

The core material formed in this manner is not particularly limited as long as it is an aggregate of monofilaments as described above, but it may be a heated thread.

As for the heating conditions at this time, the denier number varies depending on the number of filaments, but for example, 1200 denier 1
In the case of 170 filament yarn, it is preferable to use it by twisting 25s and 12z and doubling.

The strength is further improved by heating.

In addition, when using it as a core material, monofilaments may be assembled or knitted (this can also improve the strength.

Even in such processing, there is no problem because the bending properties, fatigue resistance, and wear resistance are sufficient.

Furthermore, it is preferable that the belt has sufficient bending characteristics such as loop strength and knot strength for use as a conveyor belt.

Since the above-mentioned fibers are used as an aggregate as described above, adhesion between the fibers is required, but the adhesion in this case is sufficient.

Furthermore, although the adhesion between the belt base made of hard urethane resin and the like and the above-mentioned fibers is almost sufficient, it is preferable to pre-treat the above-mentioned fibers by plasma discharge or corona discharge in order to increase the adhesion. Furthermore, if necessary, it is preferable to perform a brimer treatment, and preferred examples include epoxy resin coating, modified polyethylene resin coating, and modified polyethylene and epoxy resin coating.

Furthermore, for long-term use, it is also preferable to have excellent creep properties, and from this point of view, it is preferable to use Guineema 5K60 spun using a volatile solvent. In general, fibers spun using non-volatile solvents such as paraffin have some drawbacks in creep properties, but in the method of use of the present invention, this is not so much of a problem, and even materials such as Techmilon can be used satisfactorily.

A conveyor belt having an ultra-high strength polyethylene fiber as a core material can be produced as follows.

For example, predetermined filament yarns of commercially available fibers may be twisted or twisted.

Such a core material is set in a mold, pre-treated with corona discharge or plasma discharge as necessary, and further treated with a brimer as necessary, and then coated with a belt base material such as thermosetting urethane resin. The synthetic resin is poured and molded.

During this molding, heat and pressure are applied to the core material,
Since the resistance against these is sufficient, the performance as a core material does not deteriorate.

By such a method, a belt having a predetermined shape as shown in FIGS. 1 and 2, for example, can be obtained.

In addition, after forming a band-like object, it is finally connected to form an endless belt.

In addition, in the present invention, the polyvinylidene fluoride resin fiber used as the core material is, for example, Fora
flon(Produits Chimiques.

Ugine Ku (formerly manufactured by man) DyfloR
(manufactured by Dynamite Nobe1) KF Polymer (manufactured by Kureha Chemical Industry ■) KynaR (manufactured by Penwalt
Chemicals) Solef (Solva)
Examples include fibers obtained from products commercially available under trade names such as (manufactured by Y Company). Among these, for example,
Some fibers are commercially available as fibers under trade names such as Furehe KF Fiber (manufactured by Kureha Kagaku Kogyo ■).

Furthermore, from the viewpoint of the function as a conveying belt, specifically expressing the mechanical properties of polyvinylidene fluoride resin fibers, it is desirable that the elongation at break is 7% or more. Further, the strength is preferably 200 kg/mm'' or more, and it is desirable that the strength can be maintained at least 2 kg/mm'' when the elongation is 7% or less.

The purpose of setting such a breaking elongation is to prevent conveyance defects due to positional deviations such as the pitch of the trapezoidal protrusions of the belt being deviated from the square holes of the leagues due to elongation of the belt. Further, the reason why the strength is set as described above is to cope with tension support that is applied when a film jams.

Based on the characteristic values, it is difficult to use polyvinylidene fluoride resin fibers as long fibers (filaments) as they are in order to obtain the strength required for the core material of belts as described above, and it is difficult to use them as heating yarns. It is preferable to improve the strength etc. before use.

In addition, it may be braided or knitted.

Moreover, this fiber has good adhesion not only between the fibers but also with the belt base made of hard urethane resin or the like.

Furthermore, when producing the conveyor belt, as mentioned above,
Although molding processing is performed, the resistance to heat and pressure in this case is sufficient.

In addition, the bending properties such as creep properties and binding strength are sufficient for use as a conveyor belt.

Note that the molding method may be a known method.

Further, the conveyor belt is not limited to those shown in FIGS. 1 and 2, and the core material in the present invention is
It can be applied to either.

In addition, these ultra-high strength polyethylene fibers or polyvinylidene fluoride resin fibers are preferably embedded in the cross section of the belt base in an area of about 1 to 20% of this cross section.

As mentioned above, by using ultra-high strength polyethylene fibers or polyvinylidene fluoride resin fibers as the core material, unlike the conventional aramid fibers, there is no elution of substances that would inhibit the development performance of color developers. , images with consistent photographic performance can be obtained even during long-term continuous processing.

Therefore, in the present invention, the replenishment amount of the color developer is 700 a+j or less, preferably 100 to 700 a+j per sensitive material IC.
Although it is processed using a low replenishment method of 500 ml, unlike conventional aramid fibers, there is no problem in terms of photographic performance.

That is, since there is no formation of inhibitory substances, the frequency of replacing the replenisher with a fresh color developing solution is reduced, making it possible to reduce the amount of replenishment.

Furthermore, compared to conventional products, the strength is also improved, and the durability as a conveyor belt is improved.

This is thought to be because the strength and the like are sufficiently maintained even when the core material comes into contact with the color developer at the minute exposed portion from the base of the belt or at the seam of the belt, especially after long-term use.

Therefore, the liquid temperature is 38% lower than when using aramid fiber.
℃ and a linear speed of 60 cm/min, the belt life can be extended by 3 to 10 times. In particular, those using ultra-high strength polyethylene fibers are up to 10 times more expensive.

A conveyor belt whose core material is ultra-high strength polyethylene fiber or polyvinylidene fluoride resin fiber can be used not only in a processing tank filled with color developing solution (color developing tank), but also in other processing tanks and drying rooms. can.

In particular, it is preferable to use it in a processing tank (bleach tank) containing a high-potential oxidizing agent used for the purpose of speeding up the processing and filled with a bleaching solution used at a low pH (usually 3 to 5). Improves durability.

In addition, in order to perform rapid drying in a drying room, the drying temperature may be set to about 60 to 70°C, but even in such cases, it is desirable to use the core material in the present invention because it is highly heat resistant. .

In addition, in any treatment tank, the core material of the present invention has better chemical resistance, water resistance, etc. than conventional products, so its application is preferable, and the durability of the belt is improved.

An example of an automatic processing machine to which the conveyor belt of the present invention is applied is one having the configuration shown in FIG. 3.

As shown in FIG. 3, the outer side of the automatic processor 2 is covered with a frame 14 to block all light from the outside world. Further, the lower part of the frame 14 is supported on a floor 18 by a plurality of support legs 16.

The frame 14 has a plurality of holes extending upward and downward.

Processing tanks 20, 22, 24, 26, 28, 30, and 32 are formed, and each is partitioned by a vertical wall 33 that is a part of the frame. The processing tank 20 is filled with a developing solution, the processing tank 22 is filled with a bleaching solution, the processing tank 24 is filled with a fixing solution, the processing tanks 26 and 28 are filled with washing water, and the processing tank 30 is filled with a stabilizing solution. Reference numeral 32 constitutes a drying chamber, below which a heater 34 and a blower 35 are arranged to form a hot air supply means, so that hot air is sent upward.

Further, a guide roller 36 is provided below each type 20 to 32 and on each vertical wall, and a guide 37 corresponds to the guide roller 36 with a predetermined gap. Furthermore, various 20
Sprockets 38 are installed above and below 32, respectively, and a film conveying belt 1 having the same structure as that shown in FIGS. 1 and 2 is suspended from these sprockets 38.

On the other hand, the film S is placed on the spool 4 as shown in FIG.
4 and is housed in a cartridge 46. In the illustrated example, the leading ends of the two films S pulled out from the spool 44 are fixed to one leader 48, so that the two films S can be conveyed simultaneously.

The leader 48 is a flexible synthetic resin sheet that is slightly more rigid than the film S, and has a plurality of square holes 5 along the longitudinal direction of the center.
0. When these square holes 50 engage with the protrusions 13 of the belt 1, the film S is conveyed.

A film supply device 54 is installed on the upper entrance side of the automatic processing machine 2 (on the left side in FIG. 3), and the upper part thereof is covered with a cover that can be opened and closed.

This film supply device 54 is provided with a film pedestal 58 on which each cartridge 46 of the film S connected to the leader 48 can be placed.

A pair of conveyance rollers 6 are provided between the pedestal 58 and the guide roller 36.
0 is provided, and this conveyance roller 60 moves the leader 48 and the film S to the film conveyance bell!・Transfer to 1. A cutter 62 is installed between the pedestal 58 and the conveyance roller 60,
When the entire amount of the film S is pulled out from the cartridge 46 by a control means (not shown), the end of the film S is cut.

A film stacking device 64 is installed on the upper exit side of the automatic processor 2 (right side in FIG. 3). In this film stacking device 64, a guide 66 is connected to the end of the frame 14,
A conveyance roller 68 is provided on the lower surface of the guide 66.

A collection plate 70 is arranged at the tip of the guide 66 with a predetermined gap, and a hook 72 projects diagonally upward from the upper inner surface of the collection plate 70.

For this reason, the film S and the leader 48 that have undergone each processing step are pulled out by the conveyance roller 68, and then moved upward along the lower surface of the guide 66 and the inner surface of the accumulation plate 70, and are moved upward through the square hole 50 of the leader 48 ( (see FIG. 4) engages with the hook 72.

Therefore, the film S and the leader 48 are transported as follows.

First, the leading ends of the two films S are pulled out from the cartridge 46 and fixed to the rear end of the leader 48 as shown in FIG. Next, the cover 56 of the film supply device 54 (FIG. 3) is released, each cartridge 46 is set on the pedestal 58, and the leader 48 is placed on the conveying roller 60 below.

When the cover 56 is closed in this state, the leader 48 is held between both transport rollers 60, and when a predetermined switch is turned on, the leader 48 and the film S are sent out between the guide rollers 36 and 37.

The leader 48 and the film S are turned downward by the upper guide 37, and the square hole 50 of the leader 48 fits into the projection 13 of the belt 1.

Therefore, even if the end of the film S comes off the transport roller 60, the leader 48 and the film S are immersed in the developer in the processing tank 20 by the belt 1.

On the other hand, when the entire amount of the film S is pulled out from the cartridge 46, the cutter 62 is activated and the end of the film S is cut off from the cartridge 46.

The leader 48 and the film S descend once inside the processing tank 20, pass between the lower guide roller 36 and the guide 37, and then are reversed and conveyed upward.

Further, since a guide roller 36 and a guide 37 are provided above the standing wall 33, the leader 48 and the film S are again turned downward and sent to the next processing tank 22.

In this manner, the leader 48 and the film S pass through each of the processing tanks 20 to 32, and the film S is subjected to color development, bleaching, fixing, washing, stabilization, and drying processing. After completing each step, the leader 48 and the film S pass between the transport rollers 68 of the film stacking device 64, the lower surface of the guide 66, and the inner surface of the stacking plate 70, and are suspended from the hook 72.

The heater 34 and the blower 35 are connected to the switch (
Since the film feeding device 54 and the conveying device (sprocket 38, belt 1) are already in operation by the processing tank 32 (not shown), the processing tank 32 itself is sufficiently warmed. In addition, the air sent out from the blower 35 passes through the heater 34 and becomes warm air, and after being divided into two almost equally by the branch guide 76, the air is divided into a space 84 and a slit 82 of the cover plate 80.
It passes through and is constantly in contact with the belt surface.

In this case, the temperature and air volume of the hot air are set so that moisture from the film S is removed and curling does not occur.

After the drying process, the roller 48 and the slit 82 are sent out to the film stacking device 64 through the upper guide 37 and the guide roller 36.

The present invention is not limited to the automatic processing machine having the configuration as shown in FIG. 3, but may be of any type as long as it is of a so-called belt conveyance type.

Further, the conveyor belt in the present invention may be applied to at least a processing tank filled with a color developing solution, but it is preferably applied to all processing tanks including a drying chamber as shown in the figure.

In addition, in the illustrated example, the processing steps are color development - bleaching constant →
The processing of water washing, water washing, and stabilization was performed, and the processing tank configuration was designed according to the processing steps. However, as long as the process includes color development, there is no particular restriction, and the processing tank configuration etc. may be changed as appropriate. I can do it.

For example, it may be combined with inversion processing.

Further, in addition to the above-mentioned (1) bleaching and fixing process, typical desilvering processes include the following.

■ Bleach - Bleach-Fix ■ Bleach - Bleach-Fix ■ Bleach - Wash with Water ■ Rinse-Bleach-Fix ■ Wash with Water - Bleach-Fix ■ Bleach-Fix ■ Fix - Bleach-Fix Of these, for example, JP-A-61 −
No. 75352.

In addition, the treatment baths such as bleaching baths and fixing baths used in the above steps may have one tank or two or more tanks (for example, 2 to 4 tanks, in which case a countercurrent system is preferable). good.

In the present invention, a film-like material is mainly used as the color photosensitive material.

Such light-sensitive materials are mainly color negative films and color reversal films, which are composed of silver halide containing silver iodide. Therefore, it is preferable to apply steps (1), (2), and (2) to rapid processing of such light-sensitive materials.

In the treatment process of the present invention, a water washing or stabilization process is usually performed in combination after the desilvering process, but it is also possible to use only the water washing process, or to perform the stabilization process without actually washing with water. This can be a simple processing method.

The color developing solution 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-I N,N-diethyl-p-phenyl diamine D-22-amino-5-diethylaminotoluene 2-amino-5-(N-ethyl-N-laurylamino)toluene 4-[N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −[β
-(methanesulfonamide)ethylcoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenyl diamine D-94-amino-3- Methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above-mentioned -phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic primary amine color developing agent to be used is preferably about 0.1 to 1 j per color developer.
A concentration of about 20 g, more preferably about 0.5 to about Log.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developing solution as preservatives as necessary. be able to.

The preferable amount of preservative added is 0.5 per 1j of color developer.
~Log, more preferably 1 to 5 g.

Alternatively, the aromatic primary amine color developing agent may be directly applied to
Examples of the preserving compound include various hydroxylamines, hydroxamic acids described in JP-A-63-43138, and JP-A No. 63-43138.
Hydrazines and hydrazides described in No. 3-146041, phenols described in No. 63-44657 and No. 63-58443, α-hydroxyketones and α-aminoketones and/or α-aminoketones described in No. 63-44656, It is preferable to add various saccharides described in No.-36244. In addition, in combination with the above compounds, JP-A-63-
No. 4235, No. 63-24254, No. 63-2164
Monoamines described in No. 7, No. 63-146040, No. 63-27841 and No. 63-25654, etc.
No. 63-30845, No. 63-14640, No. 63
Diamines described in No.-43139 etc., No. 63-216
No. 47, No. 63-26655 and No. 63-4465
Polyamines described in No. 5, nitroxy radicals described in No. 63-53551, alcohols described in No. 63-43140 and No. 63-53549, No. 63-56
Oximes described in No. 654 and No. 63-239447
It is preferable to use the tertiary amines described in No.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
- Salicylic acids described in No. 180588, JP-A-54-3
Alkanolamines described in No. 532, JP-A-56-9
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
．． The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary.

Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developing solution 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.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, Q-
Thorium hydroxybenzoate (sodium samamethylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of buffer added to the color developer is 0. It is preferably 1 or more per morph, particularly preferably 1 to 0.4 mol/1 O.

In addition, various chelating agents can be used in the color developer to prevent precipitation of calcium or magnesium, or to improve the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specifically, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid,
Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2-
Phosphonobutane-1,2,4-tricarboxylic acid, l-hydroxyethylidene-1,1-diphosphonic acid, N, N'
-Bis(2-hydroxybenzyl)ethylenediamine-
N,N'-diacetic acid and the like.

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 lI
The amount is about 0.1 to 10 g per 2 pieces.

Any development accelerator can be added to the color developing solution if necessary. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means per developer solution 14 2 liters or less, preferably total (meaning not containing).

In addition, as a development accelerator, Japanese Patent Publication No. 37-16088
No. 37-5987, No. 38-7826, No. 44
-12380, No. 45-9019, U.S. Patent No. 3.
818,247, etc. 5 p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554;
Quaternary ammonium salts described in Japanese Patent Publication No. 0-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2,494
No. 903, No. 3,128,182, No. 4.23
No. 0,796, No. 3.253.919, Special Publication No. 1973
-11431, amine compounds described in U.S. Patent No. 2,482,546, U.S. Patent No. 2,596,926, U.S. Pat.
No. 42-25201, U.S. Patent No. 3,128°183
Polyalkylene oxides shown in Japanese Patent Publications No. 41-11431, No. 42-23883, U.S. Pat. can do.

In the present invention, any antifoggant can be further added as required. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitropenzimidazole, 5-nitroinindazole, 5-methylbenzotriazole, 5-
Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazotruebenzimidazole, 2-thiazolylmethyl-benzimidazole, indazole,
Representative examples include nitrogen-containing heterocyclic compounds such as hydroxyazaindolizine and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightening agent, 4,4°-diamino-2,2°-disulfostilbene compounds are preferred. Addition amount is 0 to 5 g/l, preferably 0.1 to 4 g/l
It is.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature with the color developing solution of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. When performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer includes dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-
Known black and white developing agents such as aminophenols such as p-aminophenol can be used alone or in combination.

After color development, the photographic emulsion layer is usually subjected to a darkening process. As mentioned above, the bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately.In order to speed up the process, it is also possible to perform a bleach-fixing process after the bleaching process. It is also possible to carry out treatment in two consecutive bleach-fixing baths, to carry out fixing treatment before bleach-fixing treatment, or to perform bleaching treatment after bleach-fixing treatment, depending on the purpose.

Bleaching agents used in bleach or bleach-fix solutions include, for example, iron (■), cobalt (■), chromium (Vl
), compounds of polyvalent metals such as copper (II), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (m) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3-
Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. . Of these, iron ethylenediaminetetraacetate (
III) Aminopolycarboxylic acid iron (m
) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron aminopolycarboxylate (I [
I) i-salts are particularly useful in both bleach and bleach-fix solutions. These iron aminopolycarboxylic acids (
m) A bleach solution or a bleach-fix solution using a complex salt can be processed at pi (usually 2.5 to 8).

In particular, for rapid processing of photographic color photosensitive materials such as color negative films and color reversal films, high-potential oxidizing agents with an oxidation-reduction potential of 150 mV or more, preferably 180 mV or more, more preferably 200 mV or more are used as bleaching agents. .

The redox potential of the bleach mentioned above is determined by the Transactions of the Faraday Society (Tra
actions of the FaradayS
55 (1959), 1312~
It is defined by the redox potential measured by the method described on page 1313.

The redox potential in this case was obtained by the above-mentioned method under the condition of pH 6.0.

Primarily, such high potential oxidizing agents are used in bleaching solutions, and such bleaching solutions are described below. With such a bleaching solution, the bleaching time can be reduced to 120 seconds or less, preferably 50 seconds or less, and more preferably 40 seconds or less, thereby speeding up the bleaching process.

Such bleaching agents include inorganic compounds such as red blood salt, ferric chloride, dichromate, persulfate, and bromate, and iron(III) aminopolycarboxylate [some of the salts are organic compounds]. can be mentioned.

In the present invention, aminopolycarboxylic acid iron (m) va salt is preferably used from the viewpoint of environmental protection, handling safety, metal corrosivity, and the like.

Below, the aminopolycarboxylic acid iron (I[
[) Specific examples of complex salts will be given, but the invention is not limited to these. In addition, the redox potential in the above definition will be described.

Compound no.

Redox potential (OIV vs, NHE, p[(=6j],, N-(2
-acetamide) iron(III) iminoniacetate complex 2, iron(III) methyliminodiacetate complex 3, iron(III) iminoniacetate complex 4.1.4-butylenediaminetetraacetate iron(II) complex 5, diethylenethionythyl Diaminetetraacetic acid iron(III) complex salt 6, glycol ether diaminetetraacetic acid iron(III) complex salt 7.1.3-Propylenediaminetetraacetic acid iron(10) complex salt Among these, particularly preferred are compound No.
7 1,3-propylenediaminetetraacetic acid iron(III)
It is a complex salt (hereinafter abbreviated as 1.3-PDTA-Fe(m)).
4-24253).

Aminopolycarboxylic acid iron (I[I) complex salts are used in the form of sodium, potassium, ammonium, etc. salts, but ammonium salts are preferred because they bleach the fastest.

In addition, ethylenediaminetetraacetic acid iron (I[[)m salt (EDTA-Fe(m)), which is widely used in the industry, is 110
Iris V, iron(III) diethylenetriaminepentaacetate
# salt, trans-1,2-cyclohexanediaminetetraacetic acid iron(III) salt, etc. are 80 mV, and are excluded from the above.

The bleaching solution in the present invention contains 0.2 mol of bleach or more, preferably 0.3 to 0.7 mol/
1, more preferably 0.4 to 0.6 mol/1.

By controlling the content of the bleaching agent within the above range, processing can be speeded up and bleach fog and stain can be reduced.

However, since the use of an excessively high concentration solution will actually inhibit the bleaching reaction, the upper limit of the concentration is preferably about 0.7 mol.

Note that the concentration of aminopolycarboxylic acid iron (III) M salt preferably used in the present invention is also preferably within the above range.

Further, in the present invention, bleaching agents may be used alone or in combination of two or more kinds.

When two or more types are used together, the total concentration may be within the above range.

Furthermore, in the present invention, the redox potential is 1.50 m
In addition to a bleaching agent with a voltage of V or more, a bleach with an oxidation-reduction potential of less than 150 V may be used, but the amount used is as follows:
0.0 for 1 mole of bleach with an oxidation potential of 1501V or higher.
The amount is preferably about 5 moles or less.

Examples of such substances include ferric complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid, which have an oxidation-reduction potential of 150 LV or more, especially when used in combination with aminopolycarboxylic acid iron (III) complex salts. can be mentioned.

In addition, when using aminopolycarboxylic acid iron (III) complex salt in a bleaching solution, it is not possible to add it in the form of a complex salt as mentioned above, but it is necessary to add the complex-forming compound aminopolycarboxylic acid and ferric salt ( For example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate) may coexist to form a complex salt in the bleach solution.

In the case of this complex formation, the aminopolycarboxylic acid may be added in a slightly excess amount compared to the amount required for complex formation with ferric ions, and when added in excess, it is usually 0.01.
It is preferable to use an excess in the range of A-10%.

The bleaching solution in the present invention has an acid dissociation constant (p Ka
) 2-5, the compound of 5 is 0.5 mol/i or more, preferably 0.7-3 mol/i, more preferably 1.5-2
．． Contains 5 mol/j.

The acid dissociation constant (pKa) in the present invention is generally called the acid dissociation constant, and represents the logarithm of the reciprocal of the value expressed by Ka, and is a value determined at an ionic strength of 0.1 mol/1.25°C. shows.

Such bleaching solutions have a pH of 2 to 8, generally pH 2.5 to 8.
Used in 8.

In particular, in order to speed up the treatment, the pH should be adjusted to between 2.5 and 4.
2, preferably 2.5 to 4.0, particularly preferably 2.5
-3.5, and the replenisher is usually 1.0-4.
It is better to use it as 0.

For this reason, by containing the above compound in the bleaching solution in the above range, it becomes possible to adjust the pH to the above range, particularly to a preferable range.

In addition, when the above-mentioned compounds are used together, the total amount may be within the above-mentioned range.

By including a compound having a pKa of 2 to 5.5 in this way, it is possible to eliminate bleaching fog, and it is possible to improve the increase in staining in uncolored areas after treatment.

Examples of the compound having a pKa of 2 to 5.5 include inorganic acids such as phosphoric acid, and organic acids such as acetic acid, malonic acid, and citric acid.Any of these may be used, but the above-mentioned improvements will show the effect. Acids with a pKa of 2 to 5.5 are organic acids.
Among organic acids, organic acids having a carboxyl group are particularly preferred.

The organic acid having a pKa of 2 to 5.5 may be a monobasic acid or a polybasic acid. In the case of polybasic acids, their pK
If a is in the above range of 2 to 5.5, it can be used as a metal salt (for example, sodium or potassium salt) or ammonium salt. Moreover, two or more kinds of organic acids having pKa of 2 to 5.5 can be used in combination. However, aminopolycarboxylic acids and their Fe complex salts are excluded.

Preferred specific examples of organic acids with a pKa of 2 to 5.5 used in the present invention include formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, and butyric acid. ,
Aliphatic-basic acids such as isobutyric acid, bivaric acid, aminobutyric acid, valeric acid, and isovaleric acid; amino acid compounds such as asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, and leucine; Benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy, aromatic-basic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid , aliphatic tribasic acids such as adipic acid; amino acid tribasic acids such as aspartic acid, glutamic acid, glutaric acid, cystine, and ascorbic acid; aromatic tribasic acids such as phthalic acid and terephthalic acid; citric acid Various organic acids such as polybasic acids such as

In the present invention, among these, monobasic acids having a carboxyl group are preferred, and acetic acid and glycolic acid (hydroxyacetic acid) are particularly preferred. Further, a combination of acetic acid and glycolic acid is also preferred.

When adjusting the pH of the bleaching solution to the above range, the above acid and an alkaline agent (for example, aqueous ammonia, KOH, NaOH) may be used in combination. Among them, ammonia water is preferred.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath in the present invention, if necessary. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Pat. No. 3,893,858;
Research Disclosure No. 17,129 (
Compounds having a mercapto group or a disulfide bond described in JP-A-50-14012 (July 1978), etc.
Thiazolidine derivatives described in No. 9; U.S. Pat. No. 3,70
Thiourea derivatives described in No. 6,561; JP-A-58-1
Iodide salt described in No. 6235: West German Patent No. 2.748.
Polyoxyethylene compounds described in Japanese Patent Publication No. 430, polyamine compounds described in Japanese Patent Publication No. 45-8836, bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide bond are preferred from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat.
The compounds described in No. 1 are preferred. Additionally, U.S. Pat.
, 552,834 are also preferred. 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 the fixing agent used in the bleach-fixing solution or fixing solution in the present invention include thiosulfates, thiocyanates, thioether compounds, thioureas, large amounts of iodide salts, etc. The use is common, especially ammonium thiosulfate, which is the most widely used. Further, as the preservative, sulfites, bisulfites, sulfinic acids, or carbonyl bisulfite adducts are preferable.

In the desilvering treatment steps such as bleaching, bleach-fixing, and fixing treatments of the present invention, stirring may be as strong as possible. Specific methods for strengthening the agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461, and the rotating means of JP-A-62-183461. A method of increasing the stirring effect by using a wiper blade placed in the liquid, and a method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade installed in the liquid to create turbulence on the emulsion surface. One example is a method of increasing the circulating flow rate. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the bleach accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

As described above, the present invention is carried out by continuous processing using, for example, a belt conveyance type automatic developing machine as shown in FIG.
It is preferable to have the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259.
As described in No. 257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration in the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The present invention is preferably applied to treatments where the total treatment time (excluding drying time) is short, and specifically, it is effective in treatments where the total treatment time is 8 minutes or less, and more preferably 7 minutes or less. .

In the present invention, after desilvering treatment, water washing treatment and/or
Or a stabilization treatment is applied.

The rinsing water used in the rinsing step can contain known additives, if necessary.

For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants and fungicides that prevent the growth of various bacteria and algae (e.g., intiazolone, organochlorine disinfectants, benzotriazole, etc.) , drying load, surfactant etc. can be used to prevent unevenness, or L, E, 1st, -water
Quality Criteria, Photo, S
ci, and Eng,, vol, 9°No,
6. Compounds described in p. 344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used.
Ammonium compounds, metal compounds such as Bi and Aρ, optical brighteners, chelating agents (e.g. 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides, as necessary.
A fungicide, a hardening agent, a surfactant, an alkanolamine, etc. can be used.

Further, the water washing step and the stabilization step are preferably performed by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
, water that has been deionized to have a Mg concentration of 51 mgal or less,
It is preferable to use water that has been sterilized using halogen or ultraviolet germicidal lamps.

In each of the above processing steps for color photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution may occur due to evaporation, especially when the processing amount is small or the opening area of the processing solution is large. It becomes noticeable. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The light-sensitive material in the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the emulsion layers and non-photosensitive layers. A typical example is a silver halide color photographic light-sensitive material that has a light-sensitive layer on a support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in multilayer silver halide color photographic light-sensitive materials, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the body side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

Any of these layer arrangements can be used in the color photosensitive material of the present invention, but in the present invention, the dry film thickness of all the constituent layers of the color photosensitive material excluding the support and the undercoat layer and back layer of the support is 20.0μ or less. It is preferable to achieve the object of the present invention. More preferably 1
It is 8.0μ or less. These film thickness regulations are determined by the color developing agent that is incorporated into these layers of the color photosensitive material during and after processing. By making a big impact. In particular, the increase in magenta color, which is thought to be caused by the green-sensitive color layer, is greater than the increase in color of other cyan and yellow colors. Note that the lower limit value in the film thickness regulation is desirably reduced from the above regulation to a range that does not significantly impair the performance of the photosensitive material. The lower limit of the total dry film thickness of the constituent layers of the photosensitive material excluding the support and the undercoat layer of the support is 12.0μ, and the lower limit of the total dry film thickness of the constituent layers excluding the support and the undercoat layer of the support is 12.0 μm. The lower limit of the total dry film thickness of the constituent layers is 1.0μ.

Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer.

The film thickness of the multilayer color photosensitive material in the present invention is measured by the following method.

The photosensitive material to be measured is stored at 25° C. and 50% RH for 7 days after its preparation. First, measure the total thickness of this photosensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to determine the total thickness of the photosensitive material excluding the support. The film thickness shall be . This thickness can be measured using, for example, a film thickness measuring device using a contact-type piezoelectric transducer (Anritus Electric Co., Ltd.).
td.

K-402B 5tand). Note that the coating layer on the support can be removed using an aqueous sodium hypochlorite solution.

Next, using a scanning electron microscope, take a cross-sectional photograph of the photosensitive material (magnification is preferably 3,000 times or more), measure the total thickness on the support and the thickness of each layer, and calculate the previous film thickness. Measured value of total thickness by measuring device (absolute value of actual thickness)
The thickness of each layer can be calculated by comparing the

Swelling rate of the photosensitive material in the present invention [(25°C, equilibrium swelling film thickness in H, O - dry total film thickness at 25°C, 55% RH/dry total film thickness at 25°C, 55% RH)] X1001 is 5
0 to 200% is preferable, and 70 to 150% is more preferable.

If the swelling ratio deviates from the above value, the amount of color developing agent remaining will increase, and this will have an adverse effect on photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Furthermore, the swelling rate of the photosensitive material in the present invention is defined as the saturated swelling rate, which is 90% of the maximum swollen film thickness reached when processed in a color developing solution (38°C, 3 minutes 15 seconds).
When the time required to reach a film thickness of 2 is defined as the swelling rate T1/2, it is preferable that T1/2 is 15 seconds or less. More preferably, T1/2 is 9 seconds or less.

As mentioned above, the color photosensitive material used in the present invention is
It is suitable for belt conveyance and is generally in the form of a film.

Examples of these include color negative films for general use or movies, and color reversal films for slides or television, which are color photosensitive materials composed of silver halide containing silver iodide. .

In such a color light-sensitive material, the preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodochloride, or silver iodochloride containing about 0.1 to 30 mol% of silver iodide. It is chemical silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

In addition, film-like sensitive materials include color positive film for general use or motion pictures, duplex film,
Also included are internegative films and the like.

Among these, the present invention has great effects when applied to the processing of color negative films.

Further, in the present invention, the total amount of coated silver in the photosensitive material is 5 g/m2.
In the following, the total coated silver amount is the amount of silver in the light-sensitive silver halide emulsion. , excluding colloidal silver in the yellow filter layer and antihalation layer and fine grain silver halide in the protective layer.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may be one having crystal defects or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to 110 microns (and may be a polydisperse emulsion or a monodisperse emulsion).

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure N.
o, 17643, same No. 18716 and same No. 3
07105, and the relevant parts are summarized in the table e.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

1 Yi Gukku & Qi 11 2 Sensitivity enhancer 23 pages 648 pages right column 648 pages right column 866 pages 4 Brightener 24 pages 5 Anti-fog finished, 24-25 pages 647 pages right column 868 pages 649 pages right column Pages 868-870 Filter dyes, Page 650 Left column Dye Image stabilizer Hardener Binder Plasticizer, Lubricant Coating aid, Surface active agent 13 Static inhibitor Page 25 Page 26 Page 26 Page 27 Page 2 To 27 Page Right column 650 Pages left column 651 pages left column 651 pages left column 650 pages right column 650 pages right column 27 pages 650 pages right column 872 pages 874-875 pages 873-874 pages 876 pages 875-876 pages 876-877 pages 14 Matte 878-879 Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) No, 17643, ■-〇~G, same No. 307
105, ■-C to G. As a dye-forming coupler, a coupler that provides the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development is important.Specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers include the aforementioned RD17643, ■-C.
In addition to the couplers described in the patents listed in Items 1 and 0, the following can be preferably used in the present invention.

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, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention 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 in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and representative examples include oxygen atom-eliminating two-equivalent naphthol-based couplers. 6 In addition, humidity and temperature Couplers that form cyan dyes that are fast against chromatography are preferably used, and a typical example is a coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in U.S. Patent No. 3,772,002. Phenolic cyan couplers, 2.5-diacylamino substituted phenolic couplers, phenolic couplers having a phenylureido group in the 2-position and an acylamino group in the 5-position, 5-amides described in European Patent No. 161626A These include naphthol-based cyan couplers.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Specific examples of such couplers include magenta couplers in US Patent No. 4.366237, and specific examples of yellow, magenta or cyan couplers in European Patent No. 96.570.

The dye-forming couplers and the special couplers described above may form dimers or more polymers.

Typical examples of polymerized dye-forming couplers are described in, for example, US Pat. No. 3,451,820. Specific examples of polymerized magenta couplers are disclosed in U.S. Pat.
367.282, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD17643,
The patented couplers listed in Sections 4-F are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent Nos. 2,097,140;
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.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Pat. No. 2,322,02.
It is stated in issue 7 etc. Further, the process, effects, and specific examples of latex for impregnation of a latex dispersion method as one of the polymer dispersion methods are described in U.S. Pat. No. 2,541. ．． No. 230, etc., and PCT application number JP8 regarding the dispersion method using organic solvent soluble polymers.
It is described in the specification of No. 7100492.

Examples of organic solvents used in the above-mentioned oil-in-water dispersion method include phthalic acid alkyl esters (e.g., dibutyl phthalate, dioctyl phthalate), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl). phosphates), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), Trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of 30 to 150°C, e.g. lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β - Ethoxyethyl acetate, methyl cellosolve acetate, etc. may be used in combination.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D No. 17643 page 28 and same No. 18716
It is described from the right column on page 647 to the left column on page 648.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) Coating amounts are expressed in units of g/12 of silver for silver halide and colloidal silver, and amounts expressed in units of g/m2 for couplers, additives and gelatin. The sensitizing dye is expressed in moles per mole of silver halide in the same layer.

1st layer: Halesidin prevention layer black colloidal silver 0.15 gelatin
1.5ExM-10,08 UV-10,03 UV-20,06 S o 1 v -20,08 UV -30,07 Cp d -56x 10-' 2nd layer: Intermediate layer gelatin 1.5UV- 10,
03 UV -20,06 0,07 0,004 0,07 xF-1 V-3 olv-2 Cp d -56 %, internal high AgI type, equivalent sphere diameter 0.3 scales, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin mixed particle, diameter/thickness ratio 2.5
) Silver coating amount 0.5 0.8 COX 10 3, OX 10- I Xl0- 0.11 O911 0,02 3× 10 Gelatin xS-I xS-2 xS-3 xC-I xC-3 xC-4 pd -5 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.5511, coefficient of variation of equivalent sphere diameter 20%, normal crystal, mixed twin crystals) Particles, diameter/thickness ratio 1
) Silver coating amount 0.7 Gelatin 1.26ExS-1
1XIO-' E 14 Ex C-20,08 S o l v -10,03 Cpd-55X107' 5th layer; 3rd red-sensitive emulsion layer Silver iodobromide emulsion (Ag1 10 mol%, internal high AgI type, equivalent sphere diameter 0 .7 μs, coefficient of variation of equivalent sphere diameter 30%, twin grains, diameter/thickness ratio 2) Gelatin xS-I xS-2 xS-3 xC-5 xC-6 olv-I olv-2 pd-5 6th layer : Intermediate layer gelatin pci-s pd-I pd-4 Silver coating amount 0.7 0.8 IXIO-' 3X 10-' LX 10-' 0.05 0.06 0.15 0.08 3X 10-' 1 .0 4 Type, equivalent sphere diameter 0, 3-1 coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin mixed particle, diameter/thickness ratio 2.5
) Silver coating amount 0.30 Gelatin 0.4E x S
-45X 10-' Ex S -60,3X 10''' Ex S -5,2 ' 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.55M, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin mixed grains , diameter/thickness ratio 4) Silver coating amount 0.6 Gelatin 0.8E x S
-45X 10~4 E x S -52X 10”' E x S -60,3 10,2 Cp d -53 30%, normal crystal, mixed twin grains, diameter/thickness ratio 2.0) Silver coating amount 0.85 Gelatin 1. OE x S
-42,OX 10-' ExM-52,OX 10-'ExM-80 ,02 S o 1 v -10,20 S o l v -20,05 Cp d -54X 10-' 10th layer: Yellow filter layer gelatin 0.9 Yellow colloidal silver 0.05 Cpd-10,2 Solv-10, 15 Cp d -54x 10-' 11th layer/1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.5-1 Coefficient of variation of equivalent sphere diameter 15% , octahedral particles) Silver coating amount 0.4 Gelatin 1. OE x S
-82X 10-' ExY-160,9 ExY-140,09 Solv-10,3 Cp d -54X 10-' 12th layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal High Agl type, equivalent sphere diameter 1.3-1 Coefficient of variation of equivalent sphere diameter 25%, normal crystal, twinned mixed particles, diameter/thickness ratio 4.5) Silver coating amount 0.5 [1,6 LX 10- ' 0.12 0.04 2X 10-' Gelatin xS-8 xY-16 olv-1 pa-5 13th layer: 1st protective layer fine grain silver iodobromide (average grain size 0°AgI 1 mol%) Gelatin V -3 V-4 V-5 olv-3 pd-5 0,2 0,8 0,1 0,1 0,2 0,04 3× lO~4 14th layer: 2nd protective layer gelatin 0.9 poly Methyl methacrylate particles (diameter 1.5μ) 0.2 Cp d -54x 10-' H-10,4 In addition to the above components, a surfactant was added as a coating aid to each layer.

Next, the chemical structural formula or chemical name of the compound used in Sample 101 is shown below.

V-1 V-2 V-3 V-4 V-5 / C,H.

\ SO, C, H.

olv-1 Tricresyl phosphate olv-2 Dibutyl phthalate olv-3 Bis(2-ethylhexyl) phthalate xM-1 xC-1 xF-1 xC-2 I xC-3 xY-14 ExC-4 ExY-15 nμ ExC -5 ExC-6 ExC-7 ExY-9 ExY-10 ExY-12 ExY-13 ExY-16 Cpd-1 Cpd-2 nμ xS-1 xS-2 xS-3 xS-4 xS-5 xS-6 xS-7 xS-8 Cpd-3 Cpd-4 (:, pd-5 At this time, the support of the prepared sample lot and the undercoat layer of the support were excluded (the dry film thickness of all coated layers was 17.6μ). ,
The lubrication speed T 1/2 was 8 seconds.

The total amount of silver coated was 4.5 g/m2.

The prepared sample was cut and processed into a width of 35+ am, subjected to image exposure, and then processed using an automatic processor configured as shown in Figure 1.
Continuous processing was carried out according to the following processing steps for three months at a processing rate of 301 Il per day.

However, the conveyor belt of the automatic processing machine is a conventional product, as shown in FIGS. 1 and 2, and uses aramid fiber (Kevlar) as a core material.

Processing process Processing time Processing temperature Replenishment amount ° Tank capacity Color development 3 minutes 00 seconds 37.5°C (listed in Table 1) 101 bleaching 40 seconds 38.0
℃ 4.5 resistance 51 constant t 1 minute 30 seconds 38.0℃ 30+++1 101 water washing (1) 30 seconds 38.0℃ -51 water washing (2130 seconds 38.0℃ 3h1 5
g stable concave second 38.0℃ 20a+
j 5 j Drying 1 minute 55
°C *The amount of replenishment is per 35mm width and 1m length.Water washing is a countercurrent method from (2) to (1). (1) All overflow from the tank flows into the fixing tank. Also, the developer is carried into the bleaching process. The amount of fixing solution carried into the washing process is 1 m of photosensitive material with a width of 35 mm.
They were 2.5 mg and 2.0 mg per length, respectively.

Also, the crossover time is 5 seconds in each case,
This time is included in the processing time of the previous step.

The bleaching tank and the fixing tank each had an open area ratio of 02.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (g) Replenisher (gl - Sodium hydroxyethylide sulfite 4.0 5.8 Hydrorium carbonate 40.0 40.0 Potassium bromide 1.3 (below) Hydrorium iodide 1.5 mg Hydroxylamine sulfate 2-methyl-4- [N- 2,4 3,6 ethyl-N- (β-HiH [adjusted with potassium hydroxide 10.05 (below) (50%)] In addition, in the replenisher In order to keep the tank liquid concentration constant, different values were used for the color developing agent (CD) concentration, KBr concentration, and pi (depending on the replenishment amount. The values for each replenishment amount are as follows.

950mj/m' 5.3g/j O,8
g/j 10.11700mffi/m'
5.6mg 0.6g/l 10.
1.4500mg/m2 6. Og/l 0.
3g/l 10.17400mg/m”
6.4g/l 0.05g# 10.2
0 (bleach solution) Mother solution (g) Replenisher solution (g)
1,3-Propylenediaminetetraacetic acid ferric ammonium hydrate 144.0 206.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 30.8 41.7 Acetic acid (98
%) 42 60 hydroxy vinegar @
49 Add 70 water
1000ml 1000100O [Adjusted with ammonia water (27%)] 4.35 4.0
0 (Fixer) Common to mother solution and replenisher (g) Ethylenediaminetetraacetic acid diammonium salt 18 Ammonium sulfite 20,0 Ammonium thiosulfate aqueous solution (700 g/j)
280.0ml imidazole
28 Add water
1.0j pH 7,4 (washing water) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). IRA-
400) to reduce the concentration of calcium and magnesium ions to 3 mg to 7 g or less, followed by 20 mg of sodium incyanurate dichloride.
# and 150 mg/j of sodium sulfate were added. The p[(of this solution was in the range of 6.5 to 7.5).

(Stabilizing solution) Common to mother solution and replenisher solution (unit: g) Formalin (37%) 1.2a+1 surfactant
0.4[C,. Hxl-o +co
zcuao + 1゜H1 ethylenediaminetetraacetic acid disodium dihydrate with 0.05 water added
11 pH 5, o to 7.0 Such treatment is referred to as treatment IA.

In processing IA, the same process was carried out except that ultra-high strength polyethylene (HP-PE) AM fiber (Dyneema 5K60) was used as the core material of the conveyor belt.

This is referred to as processing IB.

In this case, the conveyor belt was manufactured as follows.

Ultra-high strength polyethylene fiber (Dyneema 5K60) 1
25s of 200d 1170 filament yarn,
Three yarns are twisted at 12z, and four of these yarns are set in a mold as a core material, and thermosetting urethane resin is poured in and molded to form a material for transportation as shown in Figure 1. Got the belt.

In addition, in processing IA, polyvinylidene fluoride (PvdF) resin fiber (
The process was carried out in the same manner, except that the fibers were used as KF fibers.

This is referred to as a processing IC.

In this case, the conveyor belt was made in the same way as the ultra-high strength polyethylene fiber in Treatment IB.

In the above processing IA-IC, the replenishment amount of the color developing solution was changed as shown in Table 1, and the photographic performance and deterioration of the conveying belt were examined at the start of running and after 3 months. The photographic performance was examined in terms of gradation, and the deterioration of the conveyor belt was examined in terms of the appearance of the belt and the adhesion between the core material and the urethane resin.

The results are shown in Table 1.

These results were obtained as follows.

(1) Fuji Color Negative Film Control Strips for CN-16Q manufactured by Gradation Fuji Photo Film ■ (Code No. NM
O4) and HD (high density) and LD (
The magenta transmission density of each batch (HD-LD) was measured using a photographic densitometer FSD-103 manufactured by Fuji Photo Film Co., Ltd., and the HD-LD) value was taken as the gradation value.

(2) State of deterioration of the conveyor belt ■Appearance The state of deterioration of the belt was visually determined. In the table, ○,
Indicated by △ and X.

○: No deterioration △: Cracks in nirarethane resin ×: Cuts in belt core material ■Adhesiveness The adhesion between the urethane resin and the core material at the cracked part of the belt was visually judged. In the table, the values are indicated by ○, △, and ×.

○: Completely adhered △: Slight gap occurs to the extent that the liquid penetrates ×: There is a part where the nirarethane resin and the core material are completely separated. As is clear from Table 1, the process using the conveyor belt in the present invention In this case, even when the amount of replenishment of the color developer is reduced, there is no problem in terms of photographic performance.

In addition, in Processing IA, the same process was performed using a hanging developing type automatic processor instead of the belt conveying type automatic developing machine, and the photographic performance was examined in the same way. It has been confirmed that belts have no effect on photographic performance, although they have disadvantages in terms of larger equipment, cost, and transportation time.However, the processing of the present invention shows photographic performance equivalent to belts. Ta.

Further, the conveyor belt in the present invention has little deterioration.

In addition, in processing IA, IB, and IC, when processing was performed with the color developer replenishment amount at 950 o+j/a+",
There are almost no problems in photographic performance or belt deterioration.
showed equivalent results. This confirmed that the present invention is effective in treatment with reduced replenishment amount.

Example 2 Sample 201 was prepared by changing the amount of coated silver from Sample 101 of Example 1 as follows.

2 3rd N! 4th layer 5th layer 7th layer 8th layer 9th layer 11th layer 12H Coated silver amount (g/m'1 0.4 0.6 0.6 0.25 0.5 0.7 0.35 0.4 Total 3
．． 8 Using such sample 201, treatment I of Example 1
The same treatments as A, IB, and IC were performed, and the photographic performance and the state of deterioration of the conveyor belt were investigated in the same manner as in Example 1.

Processes 2A, 2B, and 2C correspond to the processes IA, IB, and IC of the first embodiment, respectively.

The results are shown in Table 2.

As is clear from Table 2, when a photosensitive material with a reduced amount of coated silver is used, the photographic performance deteriorates significantly with the conventional conveying belt, but this is greatly improved in the present invention.

In Processes 2A, 2B, and 2C, when the color developer was replenished at a replenishment amount of 950 ml/m'', there were almost no problems in photographic performance or belt deterioration, and the same results were obtained. From this, it was confirmed that the present invention is effective in a process in which the amount of replenishment is reduced.

<Effects of the Invention> According to the present invention, images with consistently good photographic performance can be obtained in continuous processing over a long period of time using a low replenishment method using a belt conveyance type automatic processing machine.

Moreover, the durability of the conveyor belt is also excellent.

[Brief explanation of drawings]

FIG. 1 is a perspective view showing a part of the conveyor belt in the present invention, FIG. 2a is a sectional view taken along the line 1-I in FIG. 1, and FIG. 2b is a sectional view taken along the line ■-■ in FIG. 2a. It is. FIG. 3 is a cross-sectional side view showing an example of the configuration of an automatic processor according to the present invention. FIG. 4 is a plan view of the film connected to the leader. Explanation of symbols 1... Belt 11... Belt base 13... Trapezoidal protrusion 15... Engaging protrusion 17... Core material 2... Pride 20.22.24. 26. 28. 30, 32...Processing tank 36...Guide roller 38...Sprocket 44...Suburu 46...Patrone 48...Leader 50...Square hole Patent applicant Fuji Photo Film Co., Ltd. Agent People Patent Attorney Ishii Kankan Patent Attorney
Increase 1) Tatsuya IG1 F I G, 2a IG

Claims (2)

[Claims] (1) The silver halide color photographic material is processed by an automatic developing machine having a processing tank filled with a processing solution containing at least a color developing solution, and a conveying belt provided in the processing tank for transporting the silver halide color photographic light-sensitive material. In the method for processing photographic light-sensitive materials, the core material embedded in the belt base of the conveying belt is made of ultra-high strength polyethylene fibers or polyvinylidene fluoride resin fibers, and the replenishment amount of the color developer is adjusted to halogen A method for processing a silver halide color photographic material, characterized in that the amount of silver halide color photographic material is 700 ml or less per 1 m^2 of the silver halide color photographic material. (2) The method for processing a silver halide color photographic material according to claim 1, wherein the amount of coated silver in the silver halide color photographic material is 5 g/m^2 or less.