JP3321287B2 - Processing method and processing apparatus for silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, which is simple and quick, has a small amount of processing waste liquid, and has no transport failure and no contamination of the light-sensitive material being processed. The present invention relates to a processing method and an apparatus for processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art When a silver halide photographic light-sensitive material is processed, that is, when the light-sensitive material is developed using an automatic developing apparatus, particularly a small processing machine called a minilab, a member generally called a leader is attached to the tip of the light-sensitive material. Processing. In order to simplify the mounting work of the reader, for example, in Japanese Patent Application Laid-Open No. 4-141645,
It has been proposed that guides for supporting both ends of the photosensitive material be arranged along the direction in which the photosensitive material is transported to carry the photosensitive material.

On the other hand, in recent years, from the viewpoint of environmental protection, it has been desired to reduce the discharge amount of the processing waste liquid. For example, so-called low replenishment processing for reducing the replenishment amount of the processing liquid has been performed. However, if the developing solution is replenished at a low level, the effluent from the photographic material during processing accumulates, causing a problem that the activity of the developing solution is reduced.

[0004] As means for restoring the activity of the developer,
It is generally known to raise the processing temperature of the liquid or increase the concentration of the developing agent.However, when an automatic developing device having the above-mentioned guide is used, all the transport paths from the beginning to the end of the processing are continuous. Therefore, a new problem has been found that distortion occurs due to temperature expansion and the like, and good conveyance is hindered. That is, when the temperature of the processing liquid is 40 ° C. or higher, the temperature difference between the time of the processing and the case where the temperature control is stopped after the processing is large, so that the expansion of the guide becomes a level that cannot be ignored. In the case of the guide conveyance as described above, the photosensitive material is conveyed along the guide groove such that both ends thereof are sandwiched between the guide grooves.However, the guide expands due to a rise in temperature, and distortion occurs in the processing tank. In this case, the resistance at both ends of the photosensitive material increases, and a photosensitive material having a length of usually 1 m or more generally receives a considerably large resistance. In addition, since the transport driving unit is located at a limited portion of the guide, a constant transport time cannot be maintained due to the resistance, or the transport length varies due to expansion of the guide, and the transport between the processing tanks or the turn unit is not performed. Or the timing between the drive rollers in the, the conveyance becomes unstable, and in the worst case, the photosensitive material is distorted,
There is a risk of being scratched.

When the concentration of the developing agent is increased, the developing agent or its oxidatively decomposed material tends to deposit in the groove of the guide near the interface between the processing solution and air, and as a result, the guide groove is conveyed due to clogging. It has also been found that the photosensitive material is liable to be contaminated due to defects and adhesion of deposits.

[0006]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a photosensitive material which can easily and satisfactorily convey a silver halide photographic light-sensitive material irrespective of whether or not a reader conveying method is used. An object of the present invention is to provide a material processing method and a photosensitive material processing apparatus used for the method. Further, a second object of the present invention is to provide a photosensitive material processing method and a photosensitive material processing apparatus capable of performing rapid processing without deforming a guide or causing conveyance failure even when processing is performed at a high temperature. It is in. A third object of the present invention is to discolor the guide even when a high concentration of an amine color developing agent is used,
It is an object of the present invention to provide a photosensitive material processing method and a photosensitive material processing apparatus which do not cause contamination of a photosensitive material during processing without causing clogging of a groove.

[0007]

The object of the present invention has been attained by the following means. The invention according to claim 1 of the present application relates to a method for processing a silver halide photographic material. A step of treating the material under the condition that the temperature of at least one treatment liquid is not less than 40 ° C. and not more than 50 ° C .;
Developing using a developing solution containing a developing agent of not more than 1 g / liter, and processing the silver halide photographic light-sensitive material by a guide provided along a transport direction to support both ends of the light-sensitive material. And conveying the guide, wherein the linear expansion coefficient of the member constituting the guide is 6 × 10 ⁻⁵ (cm
/ Cm ° C) or less, −1.0 × 10 ⁻⁵ (cm / cm ° C) or more, and the inner width of the guide groove is 0.5 mm or more and 5.0 mm or less, and the groove depth is 2 mm. It is not less than 5 mm.

According to a second aspect of the present invention, there is provided a silver halide having a processing tank for processing a silver halide photographic light-sensitive material, and conveying means for conveying the light-sensitive material through the processing tank by a predetermined route. An automatic conveyance processing apparatus for a photographic photosensitive material, wherein guides for supporting both ends of the photosensitive material are provided along a conveyance direction in a conveyance path of the photosensitive material, and a member constituting the guide has a linear expansion coefficient of 6 × 10 ^-5 (cm / cm
° C) or less, -1.0 × 10 ^-5 (cm / cm ° C) or more, and the inner width of the groove of the guide is 0.5 mm or more.
0 mm or less, and the groove depth is 2 mm or more and 5 mm or less.

According to a third aspect of the present invention, there is provided the apparatus for processing a silver halide photographic material, wherein the member constituting the guide includes a repeating unit represented by the following general formula (I). It is characterized by containing a polymer compound formed by coalescence.

[0010]

Embedded image

In the formula, R represents an alkyl group;
Represents an integer of 1,000,000. Hereinafter, the present invention will be described in more detail.

In the processing method of the silver halide light-sensitive material of the present invention, the activity of the developing solution is set to be high especially for rapid processing. Specifically, a developing agent concentration of 15 mm
This is a step of developing using a developing solution of not less than ol / liter and not more than 60 mmol / liter, and further a step of treating the solution at a temperature of not less than 40 ° C. and not more than 50 ° C. As for the temperature of the processing solution, it is necessary that the temperature of the processing solution in at least one processing tank is within the above range. From the viewpoint of rapid processing, the processing solution contains a developing solution. It is preferable that the concentration of the main agent is 15 mmol / L or more and 60 mmol / L or less, and the processing temperature of the developer is 40 ° C. or more and 50 ° C. or less.

If the concentration of the developing agent is less than 15 mmol / liter, it becomes difficult to rapidly process the photosensitive material, and
When the amount exceeds 1 / liter, precipitation of the developing agent becomes very easy to occur, and it becomes difficult to appropriately set the guide shape in the guide conveyance process of the present invention. Furthermore, since many developing agents are taken into the photosensitive material during development, they are not sufficiently washed out in the post-bath treatment, remain in the photosensitive material, and may adversely affect the image. Not preferred.
Further, when the temperature of the processing liquid is less than 40 ° C., rapid processing becomes difficult, and when the temperature exceeds 50 ° C., it is difficult to control the temperature difference distortion and the deterioration of the material in the guide transport processing, and The deterioration of the developer is also remarkable, which is not preferable.

Further, in the processing method of the present invention, a member having a linear expansion coefficient most suitable for the above-mentioned processing conditions of the present invention is used as a guide, so that processing of a photosensitive material under the conditions of the present invention is simple and rapid. It was found that the photosensitive material had good transportability.

Specifically, the linear expansion coefficient of the member constituting the guide is 6 × 10 ⁻⁵ (cm / cm ° C.) or less, and −1.0
× 10 ⁻⁵ (cm / cm ° C.) or more, preferably
5.8 × 10 ⁻⁵ (cm / cm ° C.) or less, −0.9 × 10
⁻⁵ (cm / cm ° C.) or more. Linear expansion coefficient is 6 × 10 ^-5
If the temperature exceeds (cm / cm ° C.), stable conveyance cannot be performed due to a decrease in the dimensional accuracy of the groove due to the temperature of the processing solution, and further, the resin may be deteriorated by the high-concentration amine-based developing agent, and the durability may be reduced. -1.0 × 10 ⁻⁵ (cm / c
(m.degree. C.), the guide shrinks in the processing solution, which deteriorates the transportability of the photosensitive material. From these viewpoints, 5.8 × 10 ⁻⁵ (cm / cm ° C.) or less, −
It is preferably 0.9 × 10 ⁻⁵ (cm / cm ° C.) or more.

In order to achieve the effects of the present invention, it is preferable to use, as a member constituting the guide, a polymer compound formed of a polymer containing a repeating unit represented by the following general formula (I). .

[0017]

Embedded image

In the formula, R represents an alkyl group, and n is 10 to
Represents an integer of 1,000,000. Here, examples of the alkyl group represented by R include a methyl group, an ethyl group, and a propyl group, and a methyl group is particularly preferable. Specific examples of the polymer compound include a polyphenylene ether resin (hereinafter, referred to as PPE) such as a compound having poly (2,6-dimethylphenylene oxide) as a main component, and a polyphenylene oxide resin (hereinafter, referred to as PPO). No. The polymer compound formed of a polymer containing a repeating unit represented by the general formula (I) may be used alone as a homopolymer, or may be modified with another resin,
A polymer alloy may be used.

Examples of the polymer alloy include a polymer alloy with a styrene resin, a polyamide resin (PA), a polyolefin resin, a polybutylene terephthalate resin, a polyphenylene sulfide resin, and the like.
In the present invention, the polymer alloy refers to a polymer multi-component system in which different kinds of polymers coexist microscopically, including a block copolymer, a graft copolymer, and a polymer blend. Specifically, the polymer alloy is preferably a modified polyphenylene ether alloyed with a styrene-based resin (hereinafter, referred to as modified PPE) or a modified polyphenylene oxide (hereinafter, referred to as modified PPO), including a styrene-grafted polyphenylene ether resin. Examples of commercially available products include "NORIL (trade name)" manufactured by Nippon GE Plastics, "Zylon (trade name)" manufactured by Asahi Kasei Corporation, and "UPIACE (trade name)" manufactured by Mitsubishi Gas Chemical Company. As polymer alloys with PA such as nylon, "Zylon (trade name)" and "Linex A (trade name)" manufactured by Asahi Kasei Corporation, and "Sumitomo SP" manufactured by Sumitomo Chemical Co., Ltd.
A), "Artry", Mitsubishi Yuka's "Remalloy" and the like, as a polymer alloy with polyolefin resin such as polypropylene and polybutylene terephthalate resin,
"UPIACE" manufactured by Mitsubishi Gas Chemical Company, "Dialoy" manufactured by Mitsubishi Rayon Co., Ltd., and polymer alloys with polyphenylene sulfide resin and the like include "UPIACE" manufactured by Mitsubishi Gas Chemical Company, respectively.

Among these polymer alloys, those particularly preferably used in the present invention include polymer alloys of modified PPE modified with a styrene resin, modified PPO, and polyphenylene sulfide resin (hereinafter referred to as PPS). Can be

The modified styrene PPE, modified PPO or P
The PE / PPS polymer alloy has a high content of PPE component.
Therefore, the coefficient of linear expansion changes. That is, in the general formula (I),
The content of polyphenylene ether represented is reduced
The linear expansion coefficient increases as the coefficient increases. Unmodified polyphenylene ae
The coefficient of linear expansion of tell is 2.7 × 10^-Five~ 3.1 × 10^-Five(C
m / cm ° C), but the thermal denaturation temperature is as high as 193 ° C.
Denaturation with styrene due to moldability problems
It uses polyphenylene ether. styrene
The linear expansion coefficient tends to increase as the mixing ratio of
6.0 × 10 ^-Five(Cm / cm ° C), the present invention
Can not be applied to In this case, the styrene mixing ratio
To lower the coefficient of linear expansion by adjusting the glass fiber and filler
Can also reduce the coefficient of linear expansion.
Wear.

In the present invention, the linear expansion coefficient of the member constituting the guide is 6 × 10 ⁻⁵ (cm / cm ° C.) or less, and −1.
It is necessary that the temperature be 0 × 10 ⁻⁵ (cm / cm ° C.) or more. However, in order to obtain desired workability and thermal characteristics, various modifications are made to the resin serving as the base material, or two or more resins are used. When a polymer alloy is prepared in the above manner, if the coefficient of linear expansion is out of the above range, it is not preferable as a member constituting the guide. Therefore, by adding a glass fiber or an inorganic filler to the polymer compound, a desired coefficient of linear expansion can be obtained. Need to adjust to the range. For example, when PPE is denatured with polystyrene (hereinafter, referred to as PS), the linear expansion coefficient and the heat distortion temperature change as follows by adding glass fiber (GF). Here, the coefficient of thermal expansion is ASTM D696, and the thermal deformation temperature is A
It was measured with STMD648 (18.6 kg / cm).

Linear expansion coefficient Thermal deformation temperature Unmodified PPE 2.7 to 3.1 × 10 ⁻⁵ cm / cm ° C. 193 ° C. Modified PPE (without filler) 7.5 × 10 ⁻⁵ cm / cm ° C. 100 ° C. Modified PPE (GF 10% reinforcement) 5.0 × 10 ⁻⁵ cm / cm ° C. 100 ° C. Denatured PPE (GF 20% reinforcement) 4.0 × 10 ⁻⁵ cm / cm ° C. 103 ° C. Denatured PPE (GF 30% reinforcement) 3.0 × 10 ^-5 cm / cm ° C. 105 ° C. When a polymer containing a polymer containing a repeating unit represented by the general formula (I), which is suitably used as a member constituting the guide of the present invention, is modified with PS, When the glass fiber or the inorganic filler as described above is not used, the content of the modified PS should be reduced as far as the desired modified property can be secured with respect to the base material PPE. Is preferred . FIG. 5A shows an infrared absorption spectrum of a PS modified PPE having a coefficient of linear expansion of 5.3 × 10 ⁻⁵ cm / cm ° C., and FIG.
3 shows an infrared absorption spectrum of PS-modified PPE at 10 ⁻⁵ cm / cm ° C. As shown in FIG. 5, the content of PS can be known by comparing the heights of the first absorption peaks of PS and PPE in the infrared absorption spectrum analysis. In the spectrum, the peak based on PPE is indicated by x, and the peak based on PS is indicated by Δ. In the case where a resin to which a filler of PS-modified PPE is not added is used as the guide member, FIG.
As shown in the figure, the first absorption peak of the PPE spectrum is PS
It is more preferable to use a resin larger than the first absorption peak of the above as a member.

The same applies to a polymer alloy with a polyamide-based resin. A polymer alloy obtained by adding a polyamide-based resin such as 6-nylon to PPE is also used. By adjusting to the range, it can be used as a member constituting the guide of the present invention. However, in the case of a polymer alloy with a polyamide resin, if the content of the polyamide resin is high, the water absorption increases, which affects the dimensional accuracy.

A polymer alloy with a polyolefin resin such as polypropylene or a polybutylene terephthalate resin has a lower water absorption and a higher impact resistance than a polymer alloy with the polyamide resin, so that the guide of the present invention can be used. It can be used for constituent members. Also in this case, it is necessary to adjust the compounding amount of each resin or to add a filler so as to obtain a preferable linear expansion coefficient.

The polymer alloy of PPE and PPS has a small decrease in physical properties and can be suitably used as a member constituting the guide of the present invention.

As described above, when a material having a suitable coefficient of linear expansion is selected from resins having high linear productivity as members constituting the guide of the processing apparatus of the present invention, the repetition represented by the general formula (I) is repeated. A polymer compound formed of a polymer containing units is preferable, and in particular, modified PPE, PPE / PP
An S polymer alloy is preferable, and a modified PPE / PPS polymer alloy is also preferably used from the viewpoint of improving moldability.

The guide used in the processing method of the present invention has an inner width of the guide groove of 0.5 mm or more and 5.0 mm or more.
Or less, preferably 1.0 mm or more and 3.0 mm
It is as follows. When the inner width of the groove of the guide is less than 0.5 mm, in the vicinity of the interface between the processing liquid and air, the processing liquid or its oxide is deposited, and the groove is easily clogged,
If it exceeds 5.0 mm, it is not preferable because the stability of conveying the photosensitive material is deteriorated. Further, the groove depth of the guide is 2 mm or more and 5 mm or less, preferably 2.5 mm or more,
It is 4.5 mm or less. If the groove depth is less than 2 mm,
The photosensitive material is apt to be separated from the guide, and if it exceeds 5 mm, it is not preferable because the image portion of the photosensitive material is damaged or the resistance during transport is unnecessarily increased.

If necessary, the guide may be formed with a corner R at the groove entrance or inside the groove, or a putty may be provided to smooth the forming angle. By chamfering the corners of the guide grooves with a chamfer of 0.1R or more and smoothing them, it becomes easier to prevent deposits and oxides of the high-concentration developing agent from being deposited, and the photosensitive material is less likely to be damaged. preferable.

In particular, it is most preferable that the guide is processed into a shape satisfying the above conditions by using a polymer compound formed of a polymer having a repeating unit represented by the general formula (I).

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a processing apparatus for a photosensitive material suitable for the processing method of the present invention will be described with reference to specific examples, but the processing apparatus of the present invention is not limited to these specific examples.

FIG. 1 shows an automatic developing machine 10 according to the present invention. The outside of the automatic developing machine 10 is covered with a frame 12 and is shielded from light. The lower part of the frame 12 is supported on the floor 16 by a plurality of support legs 14.

From the bottom of the frame 12, a plurality of standing walls 18
And a developing tank 20, a bleach tank 22, a fixing tank 24, washing tanks 26 and 28, and a stabilizing tank 30 are formed, and a processing liquid is stored in each tank (hereinafter collectively referred to as necessary). Processing tank 32).

A film loading section 34 is provided on the left side of the processing tank 32 (development tank 20) in FIG. The film loading section 34 is provided with a holding section 38 for holding a patrone 36, and the patrone 36 held on the holding section 38 is provided.
The negative film 40 pulled out of the roller is pinched by a pair of rollers 42, wound around a roller 46, and transported to the processing tank 32. A cutter 44 is arranged on the downstream side of the holding unit 38, and when the negative film 40 is completely pulled out from the patrone 36, the cutter 44 operates to cut.

As shown in FIG. 2, each processing tank 32 has:
Each of the processing racks 33 is disposed in a state where it is immersed in each processing liquid except for an upper part thereof.

As shown by a two-dot chain line in the developing tank 20 of FIG. 1, the processing rack 33 has guide grooves 33A (40, which are slightly wider than the wall thickness of the negative film 40). And some gaps between them). Although not shown, the guide groove 33A is also provided in a processing rack 33 arranged in another processing tank 32. Along the guide groove 33A, the negative film 40 is guided in each processing tank 32 in a substantially U-shape. These guide grooves 33A need not be continuous along the film transport direction, but may be provided intermittently.

A transport roller 45 composed of a large-diameter roller 45A and a pair of small-diameter rollers 45B is disposed near the liquid surface, near the bottom, and in the middle of the processing rack 33, respectively. The negative film 40 fed along 33 </ b> A is pinched to apply a conveying force.

Two rollers 45C are further disposed around the large-diameter roller 45A of the transport roller 45 located at the bottom, so that the negative film 40 can be stably turned. Each of these rollers preferably changes its outer diameter at a different position in the axial direction so as to come into contact with the film 40 only in the vicinity of the perforations at both ends in the width direction, which are off the image plane.

A portion located above the processing rack 33, that is, above the liquid level is a crossover portion, and is provided by transport rollers 47 provided on the outlet side and the inlet side of two adjacent processing racks 33, respectively. It is configured. Each of these transport rollers 47 is composed of a large-diameter roller and a small-diameter roller, so that the negative film 40 is reliably transferred to the next processing rack 33.

Thus, the negative film 40 is guided by the guide grooves 33A while receiving the conveying force from the conveying rollers 45, and is processed by each processing liquid while being conveyed in a substantially U-shape in each processing tank 32. It is discharged from 30 and delivered to the drying section 56 in the next step.

A space is formed below the stabilization tank 30,
A heater 50 and a blower 52 are provided to form a hot air supply unit, and supply hot air to a drying unit 56 located downstream of the processing tank 32 via a duct 54.

In the drying section 56, the negative film 40 is guided and conveyed by a guide roller 48 and a guide member 49 in a substantially U-shape, and is exposed to warm air during the conveyance to dry the negative film 40.

The negative film 40 having been subjected to the drying process by the drying section 56 is sandwiched between a pair of rollers 64. The roller pair 64 is rotated by the driving force, and the negative film 40 is sent to the discharge unit 66 by the rotating force.

FIG. 2A is an enlarged view of the developing tank 20 of the photosensitive material processing apparatus of the present invention, and FIG. 2B is an enlarged sectional view taken along line BB of FIG. 2A. FIG. 3 is a schematic perspective view showing a part of each of the jet blowing means and the conveying guide groove used in the developing tank 20 of FIG. Actually, the jet blowing means and the conveying guide groove are arranged closer than the illustrated state. As shown in FIG. 2 (a), the U
An upstream-side chamber 102 and a downstream-side chamber 104 are provided outside the letter-shaped movement trajectory. The lower ends of these chambers 102 and 104 are communicated with each other by a connecting cylinder 106, and the connecting cylinder 106 is communicated with a bottom opening 116 of the frame 12 through a hanging cylinder 108, and the bottom opening 116 is connected to a pressure feed pump (not shown). Are in communication.
As a result, the hanging cylinder 108 feeds the developer in the developing tank 20 into the chambers 102 and 104 under the pressure of the pressure pump.

The film 40 in the chambers 102 and 104
Slit plates 112 and 114 are fixed facing the side through which the air passes, and slit-shaped jet stirring outlets 82 having a longitudinal direction as shown in FIG. The developing solution in the chambers 102 and 104 is passed in the direction of the arrow A to the emulsion surface of the film 40, and is disposed correspondingly between the driving rollers 45A and 45B for driving the film 40. . As shown in FIGS. 2A and 3, the chambers 102 and 104 have concave portions 102 </ b> A and 104 </ b> A formed in a portion where the driving roller 45 </ b> B is located.
5A and 45B are accommodated.

A plurality of guide plates 120 and 122 having a U-shape in plan view are fixed to the slit plates 112 and 114, respectively. The passage portions 124 and 126 are formed. Plates 130 and 132 constituting the guide groove 33A are disposed in the passage portions 124 and 126 corresponding to the front and back surfaces at both ends in the width direction of the film 40 passing therethrough. It is fixed to the plates 120, 122. The pair of guide plates 120 and 122 are connected by a communication cylinder 135 at appropriate positions in the vertical direction so as not to interfere with the large-diameter drive roller 45A. These guide plates 120 and 122 are vertically separated so as not to interfere with each roller as shown in FIG. 3, but if they are formed so as not to interfere with each roller, they are continuously arranged vertically. You may.

Guide plate 12 constituting guide groove 33A
0, the materials of the plates 130 and 132 are those having resistance to various processing solutions of the photosensitive material, and have a linear expansion coefficient of 6 × 10 ⁻⁵ (cm / cm ° C.) or less and −1.0 × 10 5
Any material can be used as long as it is at least ^-5 (cm / cm ° C.). Specifically, polyphenylene ether resin (for example, Zylon manufactured by Asahi Kasei Corporation), modified polyphenylene oxide resin (for example, Nippon GE Plastics) Noril), rigid polyvinyl chloride resin (for example,
Hishi plate manufactured by Mitsubishi Plastics Chemical Co., Ltd.), and in particular, the various materials described in detail in this specification can also be suitably used. It is preferable to use a material which can be easily processed and has high durability.

In this embodiment, the plates 130, 13 are provided on a plurality of U-shaped guide plates 120, 122, respectively.
2 are fixed to form a U-shaped groove 33A for accommodating an end portion in the film width direction between these plates 130 and 132, but various modifications are possible as the configuration of the guide groove 33A. The U-shaped groove serving as the guide groove 33A may be integrally formed of a single material, for example, by extrusion molding or the like.

The jet stirring is performed in the chambers 102, 10
4 is sprayed at a substantially right angle toward the film 40 passing through the openings 82 formed in the slit plates 112 and 114 for closing the slits 4. The jetting direction of the jet agitation near the liquid surface is more perpendicular to the transport direction of the film 40 than the liquid surface W.
Inclined far away from In order to improve the effect of the jet agitation, that is, to prevent the vibration and bending of the film 40 and to ensure that the jet agitation is blown to the emulsion surface of the film 40, the film 40 is opposed to the jet agitation opening. The communication cylinder 135 is provided at a position where the communication tube 135 is located, and functions as a partition.

When the method and apparatus for processing a silver halide photographic light-sensitive material of the present invention are applied to rapid processing using a small-sized processing apparatus, the effect is remarkably exhibited. here,
A small processing unit is a 35 mm
X 60 to 5 per hour for 24 film sizes
Refers to a processing device capable of performing the main processing, preferably 1
Refers to a processing apparatus having a processing capacity of 50 to 10 pieces per hour.

FIG. 4 shows another embodiment of the jet stirring means. In the above embodiment, the mode in which the jet agitation is performed from the outside of the U-shaped movement trajectory of the film is shown. However, FIG. 4A shows that the jet agitation is performed from between the films 40 which draw the U-shaped movement trajectory. FIG. 4B is a longitudinal sectional view showing one embodiment of a processing tank in which the emulsion surface of the film 40 faces the inside of the U-shaped movement trajectory. FIG. 4B shows a transport path of a film guided by a guide. FIG. FIG.
(A) shows a cross section of the plates 130 and 132 constituting the guide groove 33A. In addition, rubber transfer rollers (drive rollers) 45A and 45B are provided at several places along the transfer path of the guide groove 33A. These are rubber rollers having a width of about 3 mm fixed to the drive shaft and corresponding to the perforated portions at both ends outside the image range of the film as shown in FIG. The film 40 is driven. The drive rollers 45A and 45B made of rubber are installed so as to contact only near guide holes at both ends of the film 40 and not to contact the emulsion surface.

A box 80 having an opening 82 as a means for jet stirring is arranged between U-shaped movement trajectories of the film as shown in FIG. 4A, and is not shown by a pipe communicating in a direction perpendicular to the plane of the drawing. It is connected to the pressure pump. An opening 82 of the box body 80, that is, a jet agitating blowout port 82 having a horizontal longitudinal direction is disposed between the upper and lower drive rollers 45A. The developer in the developing tank 20 is pressure-fed into the box 80 by the pressure of the pressure pump, and the film 40 is fed through the opening 82 of the box 80.
Is sprayed in the direction of arrow A toward the emulsion surface inside the U-shaped movement locus of the liquid crystal. The opening near the processing liquid level W is the processing liquid level W.
It is inclined toward the direction away from.

In this embodiment, the film 40 is held at both ends by the guide grooves 33A and is stably conveyed. However, the bending of the film 40 due to jet agitation is prevented, and the stability of the film 40 is improved. If desired, a freely rotatable roller may be placed in contact with the film 40 or slightly away from the emulsion side of the film 40 at a position opposite to the jet agitating nozzle 82, as desired (see FIG. 4). The roller 82 </ b> A shown by a line) can support the bending of the film due to jet agitation. The driving of the film 40 is performed by rubber driving rollers 45A and 45B. However, other rotating bodies such as a driving gear can be used instead of the rubber rollers as long as they do not come into contact with the emulsion surface.

As a modified example of the means for performing jet stirring, there is a small jet stirring apparatus in which a processing liquid supply pipe connected to a processing liquid pressure pump is connected to a small box provided with a slit. By attaching a desired number and a desired jetting direction of a small jet stirrer provided with only one slit to a desired attachment position in the treatment layer,
Jet stirring conditions can be easily adjusted.

Since jet stirring is performed on the photosensitive material guided at both ends by the guide, depending on the jet stirring conditions,
There is also a possibility that the photosensitive material is bent or detached from the guide. For this reason, it is preferable to provide a wall as a surface facing the jet agitating blowing direction to support the film. The wall may be a flat guide or a freely rotatable roller arranged at a position where it can be blocked so that the photosensitive material is not separated from the guide by the jet pressure of jet stirring. For the same purpose, it is also effective to perform the second jet stirring from the direction opposite to the jet stirring jetting direction to prevent the photosensitive material from bending.

As described above, the jet stirring is preferably performed at the initial stage of swelling in the developing solution in the case of the developing tank 20 in particular.
It is preferable that the jet agitation is close to the surface of the processing solution, and that the first jet stirring is performed within 15% of the processing time of the photosensitive material in the processing solution, more preferably within 10 to 3%. .

In each of the embodiments, the guide groove and the jet stirring means of the present invention are applied to the developing tank, but can be suitably applied to any processing tank in the processing apparatus. From the viewpoint of processing efficiency, these are preferably used in the developing step, the desilvering step or the washing step, and furthermore, two or more of these processing steps (processing tanks), particularly both baths in the developing step and the desilvering step Is preferably used.

In the following, examples of various processing agents and photosensitive materials which can be used in the method and apparatus for processing the photosensitive material of the present invention will be described, but the processing agents and the like which can be used are not limited to these. It is not something to be done.

The color developer used in the photosensitive material processing apparatus of the present invention will be described. A known aromatic primary amine color developing agent can be used in the color developer used in the light-sensitive material processing apparatus of the present invention. Preferred examples are p-phenylenediamine derivatives, and typical examples are N, N-diethyl-p-phenylenediamine, 2-methyl-N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene. , 2
-Amino-5- (N-ethyl-N-laurylamino) toluene, 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- ( β-hydroxyethyl) amino] aniline, 4
-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline, 4-amino-3-methyl-N
-Ethyl-N- [β- (methanesulfonamido) ethyl] -aniline, N- (2-amino-5-dienylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p-phenylenediamine, 4- Amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-
Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline, 4-amino-3-methyl-N-ethyl-
N-β-butoxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3
-Hydroxypropyl) aniline and the like, or a color developing agent represented by the general formula (I) in JP-A-4-443. In particular, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline, 4-amino-3-methyl-N-ethyl-N- (4
-Hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- [β
-(Methanesulfonamido) ethyl] -aniline is preferably used.

These p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, p-toluenesulfonate and the like.

The concentration of the aromatic primary amine developing agent used in the present invention must be 15 mmol or more and 60 mmol or less per liter from the viewpoint of rapid processing, and is 20 to 50 mmol / liter. Is preferred.

As a developing agent, it is particularly preferable to use 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline.

In practicing the present invention, it is preferable to use a color developer which does not substantially contain benzyl alcohol. Here, "substantially not contained" means preferably 2 ml / liter or less, more preferably 0.5 ml / liter.
Per liter or less, most preferably not containing any benzyl alcohol.

The color developing solution used in the light-sensitive material processing apparatus of the present invention may contain an organic preservative in place of or in addition to hydroxylamine and sulfite ions.

As used herein, the term "organic preservative" refers to any organic compound which, when added to a processing solution for a color photographic light-sensitive material, reduces the deterioration rate of an aromatic primary amine color developing agent.
That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which various hydroxylamines described in JP-A-63-5341, JP-A-63-106655 or JP-A-4-144446. Derivatives (excluding hydroxylamine), JP-A-63
Hydroxamic acids described in JP-A-43138;
Hydrazines and hydrazites described in JP-A-146041, phenols described in JP-A-63-44657 and JP-A-63-58443, and α- described in JP-A-63-44656.
Hydroxyketones and α-aminoketones, 63-3
Various sugars described in No. 6244 can be used in combination. Also, in combination with the above compound, JP-A-63-423
No. 5, 63-24254, 63-21647,
Monoamines described in JP-A-63-146040, JP-A-63-27841, and JP-A-63-25654;
Nos. 0845, 63-14640 and 63-431
No. 39, polyamines described in JP-A-63-21647, JP-A-63-26655 and JP-A-63-44655, quaternary ammonium salts, and JP-A-63-535.
The nitroxy radicals described in No. 51, 63-431;
Alcohols described in No. 40 and 63-53549, oximes described in 63-56654, 63
Tertiary amines, diamide compounds, condensed amines, and the like described in JP-A-239947 are particularly effective organic preservatives.

Other preservatives are described in JP-A-57-44.
148 and 57-53749, salicylic acids described in JP-A-59-180588,
JP-A-63-239647 and JP-A-63-128340.
, Amines described in JP-A-1-186939 and JP-A-1-187557, alkanolamines described in JP-A-54-3532, JP-A-56-94349.
No. 3,741.
An aromatic polyhydroxy compound described in US Pat. No. 6,544 or the like may be used as necessary. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as N, N-diethylhydroxylamine and N, N-di (sulfoethyl) hydroxyamine,
Hydrazine derivatives such as N-bis (carboxymethyl) hydrazine (excluding hydrazine). Alternatively, addition of an aromatic polyhydroxy compound represented by sodium catechol-3,5-disulfonate is preferred.

Particularly, hydroxylamines represented by the general formula (I) of JP-A-3-144446 are preferred, and among them, compounds having a sulfo group or a carboxy group are preferably used.

In the color developer used in the light-sensitive material processing apparatus of the present invention, chloride ions are contained in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10
It is preferably contained at ^-1 mol / liter. Particularly preferably, it is 3.5 × 10 ⁻² to 1 × 10 ⁻³ mol / l.

For use in the photosensitive material processing apparatus of the present invention,
3.0 × 10 ^{−5 to} 1.0 × 10 ⁻⁵ bromine ion in color developer
It is preferably contained at a rate of × 10 ^-1 mol / liter. More preferably, it is 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / liter.

Here, chlorine ions and bromine ions may be directly added to the color developer, or may be eluted from the photosensitive material into the color developer during the development processing.

When directly added to a color developer, sodium chloride, potassium chloride,
Ammonium chloride, lithium chloride, magnesium chloride,
Calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developer. Sodium bromide, potassium bromide,
Ammonium bromide, lithium bromide, magnesium bromide,
When calcium bromide is eluted from the light-sensitive material during a development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the light-sensitive material processing apparatus of the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developer includes other known developer components. Can be included.

To maintain the pH, it is preferable to use various buffers. Buffers include carbonates, phosphates, borates, tetraborates, hydroxybenzoates,
Glycylic acid, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate,
-Amino-2-methyl-1,3-propanediol salt,
Valine salts, proline salts, trishydroxyaminomethane salts, lysine salts and the like can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are excellent in solubility, buffering ability in a high pH region of pH 9.0 or more, and have an effect on photographic performance even when added to a color developer. It has the advantage that it is inexpensive without adverse effects (such as fog) and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned.

The amount of the buffer added to the color developer is
It is preferably at least 0.1 mol / l, particularly preferably from 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developer as an inhibitor for preventing precipitation of calcium or magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N-bis (2-
(Hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, hydroxyethyliminodiacetic acid and the like.
These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

An optional development accelerator can be added to the color developer if necessary. As a development accelerator, JP-B-37
-16088, 37-5987 and 38-782
No. 6, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247;
No. 15554, p-phenylenediamine compound, JP-A-50-137726, JP-B-44-300
No. 74, JP-A-56-156826 and JP-A-52-43
Quaternary ammonium salts such as those described in U.S. Patent Nos. 429 and 429; U.S. Patent Nos. 2,494,903, 3,128,182, 4,230,796, and 3,253,919; No. 2,482,546.
Nos. 2,596,926 and 3,582,346
Compounds described in JP-B-37-16088
No. 42-25201, U.S. Pat. No. 3,128,1
No. 83, Japanese Patent Publication No. 42-11431, No. 42-2388
No. 3 and U.S. Pat. No. 3,532,501, etc., polyalkylene oxides and other 1-phenyl-3-
Pyrazolidones, imidazoles and the like can be added as needed. Benzyl alcohol is as described above.

The color developing solution used in the light-sensitive material processing apparatus of the present invention may optionally contain an optional antifoggant. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6
-Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
Nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adanine can be mentioned as typical examples.

The color developing solution used in the light-sensitive material processing apparatus of the present invention preferably contains a fluorescent whitening agent.
4,4′-diamino-2,2′-
Disulfostilbene compounds are preferred. The addition amount is 0
It is 5 g / liter, preferably 0.1 g to 4 g / liter.

If necessary, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid and polyalkyleneimine may be added.

The developer is preferably subjected to a low replenishment process, preferably from 75 to 300 ml, more preferably from 75 to 250 ml, per m ^{2 of the} silver halide photographic material.

The processing temperature of the color developer used in the light-sensitive material processing apparatus of the present invention is 40 ° C. or higher and 50 ° C. or lower, preferably 43 ° C. to 50 ° C. According to the method of the present invention, the processing can be performed in a processing time of 20 seconds to 2 minutes, that is, 2 minutes or less.

After color development, desilvering is performed. In the desilvering process, the bleaching process and the fixing process may be performed separately,
It may be performed simultaneously (bleach-fixing process). In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose.

Examples of the bleaching agent used in the bleaching solution or the bleach-fixing solution include iron salts; compounds of polyvalent metal salts such as iron (III), cobalt (III), chromium (IV) and copper (II); Acids; quinones; nitro compounds and the like. Representative bleaches include iron chloride; ferricyanide; dichromate;
Organic complex salts of (III) (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc.) Persulfate; bromate; permanganate; nitrobenzenes and the like. Of these, iron ethylenediaminetetraacetate
(III) Complex salts and iron 1,3-diaminopropanetetraacetate (II
I) Iron (III) aminopolycarboxylates including complex salts
Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Ferric aminopolycarboxylate or a salt thereof is also preferred as described in page 11 of JP-A-4-144446.
Further, the iron (III) complex salt of aminopolycarboxylic acid is particularly useful in a bleaching solution and a bleach-fixing solution. A bleaching solution or a bleach-fixing solution using the iron (III) complex salt of aminopolycarboxylic acid is used at pH 3 to 8.

Known additives such as a rehalogenating agent such as ammonium bromide and ammonium chloride; a pH buffering agent such as ammonium nitrate; and a metal corrosion inhibitor such as ammonium sulfate are added to the bleaching solution and the bleach-fixing solution. can do.

It is preferable that the bleaching solution and the bleach-fixing solution contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5.5, specifically acetic acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Is common, and in particular, ammonium thiosulfate can be used most widely. Further, thiosulfates and thiocyanates, thioether compounds, also preferred combination of such thioureas.

As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in EP 294,769A2 is preferable. Furthermore, various aminopolycarboxylic acids and the like for the purpose of stabilizing the solution include a fixing solution and a bleach-fixing solution.
The addition of organic phosphonic acids (for example, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N ′, N′-ethylenediaminetetraphosphonic acid) is preferred.

The bleaching solution and the bleach-fixing solution may further contain various fluorescent whitening agents; defoaming agents; surfactants; polyvinylpyrrolidone;

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators include US Pat.
No. 93,858, West German Patent No. 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July, 1978), etc .; compounds having a mercapto group or disulfide bond; Thiazolidine derivatives described in Kaikai 50-140129; thiourea derivatives described in U.S. Pat. No. 3,706,561; iodide salts described in JP-A-58-16235; West German Patent 2,748,430 And polyamine compounds described in JP-B-45-8836; bromide ions, and the like. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 58, West German Patent No. 1,290,812,
Compounds described in -95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly useful when bleach-fixing color photographic materials for photography.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. According to the method of the present invention,
The desilvering treatment can be performed in 2 minutes or less, and the preferable time is 10 seconds to 2 minutes. The processing temperature is 25 ° C
The temperature is 50C, preferably 35C to 45C. In a preferable temperature range, the desilvering speed is improved, and the generation of stain due to the lapse of time after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. For this reason, it is particularly preferable to use the jet stirring under the conditions of the present invention in the desilvering step.

The stirring improving means such as jet stirring of the present invention is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect.

The washing solution and the stabilizing solution include hard water softeners such as inorganic phosphoric acid, polyaminocarbonic acid and organic aminophosphonic acid, metal salts such as magnesium salts, aluminum salts and bismuth salts; surfactants; A film agent or the like can be contained.

The amount of washing water in the washing step is determined by the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the washing water temperature, the number of washing tanks (the number of stages), and the replenishment method such as countercurrent, forward flow, and various others. Can be set in a wide range depending on the conditions. Further, as a solution to the problems such as the propagation of bacteria and the adhesion of generated suspended matter to photosensitive materials, which occur when the amount of washing water is significantly reduced in the multi-stage countercurrent method, Japanese Patent Application Laid-Open No.
The method for reducing calcium ions and magnesium ions described in No. 288828 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (19
1986) Sankyo Publishing Co., Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Edition, "Encyclopedia of Antimicrobial and Antifungal" (1986) A bactericide can also be used.

The pH of the washing water is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, and the like.
10 seconds at 10 ° C., preferably 15 ° C. at 25 ° C. to 45 ° C.
A range from seconds to 3 minutes is selected.

Examples of the dye stabilizer which can be used in the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. In addition, the stabilizing solution may further include a buffer for pH adjustment such as boric acid and sodium hydroxide; 1-hydroxyethylidene-1,1-diphosphonic acid; a chelating agent such as ethylenediaminetetraacetic acid; and a sulfurizing agent such as alkanolamine. Inhibitors; fluorescent brighteners; fungicides and the like can be added.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

Although the present invention can be applied to any processing tank, it is preferably a color developing tank, particularly a developer containing little or no benzyl alcohol and sulfite ions and a relatively high chloride ion concentration as described above. Effective for developing solutions.

(Example 1) The effects of the present invention will be specifically described below with reference to the results of processing of the light-sensitive material using the silver halide photographic light-sensitive material of the above example. The invention is not limited to this.

The following processing solutions were prepared. [Color developer] Ethylenediaminetetraacetic acid 4.0 g 4,5-Dihydroxybenzene-1,3-disulfonate disodium 1.0 g Potassium hydroxide 6.0 g Potassium bromide 4.0 g Potassium iodide 0.001 g Sodium sulfite 4 0.0 g Potassium carbonate 40.0 g N-methylhydroxylamine hydrochloride 4.0 g 4-Amino-3-methyl-N-ethyl-N- (hydroxyethyl) aniline sulfate 7.0 g Water was added to add 1,000 ml of pH (25 ℃ / potassium hydroxide and sulfuric acid)
10.05 [Bleaching-fixing solution] Chelating agent represented by the following general formula A
0.17mol

[0102]

Embedded image

Ferric nitrate nonahydrate 0.15 mol Ammonium thiosulfate 1.25 mol Ammonium sulfite 0.10 mol Metacarboxybenzenesulfinic acid 0.05 mol Add water 1000 ml pH (adjusted at 25 ° C./acetic acid and aqueous ammonia) 5.8 [Washing Water] Tap water is converted from an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-40).
Water through a mixed-bed column packed with 0) to reduce the concentration of calcium and magnesium ions to 3 mg / liter or less, followed by 20 mg of sodium diisocyanurate dichloride.
/ L and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5. [Stabilizing solution] 1,2-benzisothiazolin-3-one 0.1 g polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization: 10) 0.2 g Water was added to the mixture, and 1000 ml of pH (25 ° C./hydrochloric acid and aqueous ammonia) was added. 8.50) The basic steps of the development process are described below.

Processing Step Temperature Time Color development * 60 seconds Bleaching and fixing * 60 seconds Rinse (1) * 15 seconds Rinse (2) * 15 seconds Rinse (3) * 15 seconds Stable * 15 seconds Dry 80 ° C. 30 seconds * Temperature Each was changed as shown in Table 1 below.

(Washing was performed in a three-tank countercurrent system from (3) to (1).) Next, the processing apparatus shown in FIG. 1 was adjusted so as to follow the above-described processing steps, and the photosensitive material conveying guide 33A was used.
The materials and the processing temperature were varied as shown in Table 1 below, and the silver halide photographic light-sensitive material was subjected to rapid processing, and the state of conveyance was evaluated.

As the photosensitive material, a color negative film S
Using G400 (manufactured by Fuji Photo Film Co., Ltd.), processing time, occurrence of jamming of the film, and damage or breakage of the film were observed as the evaluation of the transport state. Table 1 shows the results
Shown in

[0107]

[Table 1]

As is clear from Table 1, when a guide formed of a material having a coefficient of linear expansion outside the range of the processing method of the present invention and a guide having a shape outside the range are used, the processing temperature of the present invention is reduced. It can be seen that jamming occurs frequently in the range of the method, and that the processing time is changed and the processing conditions become unstable. In particular, when the inner width of the groove of the guide is more than 5 mm or the depth of the groove is less than 2 mm, jamming or separation from the film is likely to occur,
On the other hand, when the inner width of the groove of the guide is less than 0.5 mm or the depth of the groove exceeds 5 mm, the transport resistance of the film is increased and the processing time is not stabilized, and the transport to the film is further performed. It can be seen that scratches are likely to occur. When the processing temperature was lower than the range of the present invention (No. 1), film transport was normal, but sufficient color development was not obtained with a development time of 60 seconds.

On the other hand, it can be seen that those which satisfy the conditions of the processing method of the present invention can obtain good transport performance.

(Example 2) The following processing solutions were prepared. [Color developer] Tank solution (g) Replenisher (g) Diethylenediaminetetraacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-diphosphonic acid disodium 0.5 0.5 Sodium sulfite 3. 9 3.9 Potassium carbonate 37.5 39.0 Potassium bromide 2.7- Potassium iodide 0.013- N-methylhydroxylamine hydrochloride 4.2 5.5 2-Methyl-4- [N-ethyl- N- (β-hydroxyethyl) amino] aniline sulfate (as shown in Table 2) 1000 ml 1000 ml with addition of water pH (adjusted at 25 ° C./aqueous ammonia) 4.5 4.0 [bleach] tank Liquid (mol) Replenisher (mol) 1,3-diaminopropanetetraacetic acid ferric salt ammonium monohydrate 0.33 0.50 ferric sulfate nonahydrate 0.30 4.5 Ammonium bromide 0.80 1.20 Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Add water 1000 ml 1000 ml pH (adjusted at 25 ° C./aqueous ammonia) 4.5 4.0 [fixing] Liquid] Common to tank solution and replenisher (g) Ammonium sulfite 28 Ammonium thiosulfate (700 g / L) 280 mL Imidazole 15 Ethylenediaminetetraacetate 15 1000 mL by adding water pH (adjusted at 25 ° C / acetic acid and aqueous ammonia) 5 .8 [Washing water] Tank water and replenisher common tap water is filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) Water through a mixed-bed column Processes Neshiumuion concentration below 3 mg / liter, followed by the addition of sodium isocyanurate dichloride 20mg / liter and sodium 0.15 g / l of sulfuric acid. The pH of this solution was in the range of 6.5 to 7.5. [Stabilizing solution] 1,2-Benzoisothiazolin-3-one 0.1 g Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization: 10) 0.2 g Water is added to the tank solution and the replenishing solution. 8.50) The processing steps are shown below.

[Processing step] Processing step Processing temperature Processing time Replenishment amount * Tank capacity Color development 45 ° C 90 seconds 200ml 2.0l Bleaching 45 ° C 30 seconds 130ml 0.7l Fixing (1) 45 ° C 30 seconds 100ml 7 liters Fixing (2) 45 ° C 30 seconds 70ml 0.7 liters Rinse (1) 45 ° C 15 seconds-0.4 liters Rinse (2) 45 ° C 15 seconds-0.4 liters Rinse (3) 45 ° C 15 seconds 400ml 0.4 liters stable 45 ° C. 3 seconds 70 ml 0.2 liters drying 80 ° C. 20 seconds * replenishment rate photosensitive material 1 m ² per.

(4 tank multi-flow cascade from washing (3) to fixing (2)) (2-tank multi-flow cascade from fixing (2) to fixing (1)) 1 [PVC (hard polyvinyl chloride resin): linear expansion coefficient 7.0 × 10 ⁻⁵ cm / cm ° C.] and N
o. 2 [PPE-M1 (GF 30% enhancement, modified PP
E): Using a member having a coefficient of linear expansion of 3.0 × 10 ⁻⁵ cm / cm ° C.], the processing apparatus was modified so as to satisfy the processing steps. As the photosensitive material, a color negative film S
Using G800 (manufactured by Fuji Photo Film Co., Ltd.), continuous processing was performed until the total replenishment amount of the color developing solution was 4.0 liters. The transportability of the film immediately before the completion of the treatment and the state of the scratches on the film after the treatment were evaluated. Table 2 shows the results.

[0113]

[Table 2]

As is clear from Table 2, when the concentration of the developing agent is high, discoloration of the guide and adhesion of precipitates are liable to occur near the interface between the color developing solution of the guide and air.
When a processing apparatus in which the width and depth of the groove is out of the preferable range of the present invention is used, clogging of the groove is generated, and conveyance failure and film contamination are likely to occur. On the other hand, it can be seen that when the conditions of the present invention are satisfied, good transportability can be obtained, and no damage to the photosensitive material occurs. In addition, when the active ingredient concentration was lower than the range of the present invention (Nos. 1 and 2), Example 2 was used.
No sufficient color development was obtained under the developing conditions.

(Embodiment 3) Next, an evaluation of a processing step based on a change in a guide member will be described.

The following three types of PS-modified PPE were evaluated as guide members of the same processing apparatus used in Example 1. The PS modified PPE evaluated is shown below. (In each case, PS modified PPE Zylon manufactured by Asahi Kasei Corporation was used.) (1) Zylon X302V linear expansion coefficient: 4 × 10 ⁻⁵
cm / cm ° C. (2) Zylon 220V Linear expansion coefficient: 8 × 10 ⁻⁵
cm / cm ° C. (3) Zylon 201V Linear expansion coefficient: 8 × 10 ⁻⁵
cm / cm ° C. Evaluation was performed by applying the sample to the color developer used in Example 1 at 50 ° C.
For 3 months, and the tensile strength, elongation, bending strength, and flexural modulus were measured, and the change was calculated with the value of the sample before immersion set to 100. Tensile strength and elongation are as per ASTM D63
8. Flexural strength and flexural modulus were measured according to ASTM D790. FIG. 6 shows the results.

As shown in FIG. 6, among the PS modified PPEs, the samples having a linear expansion coefficient exceeding 6 × 10 ⁻⁵ cm / cm ° C. have a significantly reduced tensile elongation at break by immersion in the treatment solution. And the material is brittle. These samples are
As shown in FIG. 6, since the change in the flexural modulus is small, in actual use, there is an inconvenience that it is delayed to find signs of deterioration of the resin. The immersion test is performed according to ASTM.
The test piece is used under no load condition, but when it is actually used as a guide for processing equipment, a mechanism for transmitting the drive is provided in addition to the guide for the photosensitive material. Etc. are more likely to occur. Furthermore, since the processing apparatus repeatedly operates and stops, the processing temperature is repeatedly increased during operation, and the temperature is repeatedly reduced during shutdown. And the fatigue of the material is accelerated.

In fact, in a processing apparatus provided with a guide made of Zylon 220V, a short photosensitive material such as a 12-shot film was conveyed for three months after the start of use, but after about three months. Therefore, the dimensional accuracy is reduced due to the deterioration of the resin of the guide member, and jamming often occurs. In addition, in the case of a long photosensitive material such as a 36-shot film, since one photosensitive material passes through a turn portion or a nip roller portion for performing a plurality of driving operations, the dimensional accuracy of the guide is reduced due to thermal expansion. , And good transport could not be performed even if less than three months after the start of use.

On the other hand, the above-mentioned Zylon is used as a guide member.
In the case of a processing apparatus using X302V, even after three months of use,
Good transport was achieved regardless of the length of the photosensitive material.

[0120]

According to the processing method of the light-sensitive material of the present invention and the processing apparatus used for the same, the silver halide photographic light-sensitive material can be easily and favorably conveyed, and the guide is deformed even when processed at a high temperature. Processing can be performed quickly without rubbing or transport failures, and even when a high-concentration amine-based color developing agent is used, the guide is not discolored and the grooves are not clogged. It shows an excellent effect that there is no contamination.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of an automatic developing machine according to the present invention.

2A is an enlarged longitudinal sectional view of a developing tank of the photosensitive material processing apparatus of the present invention, and FIG. 2B is an enlarged sectional view of a guide groove.

FIG. 3 is a perspective view of jet stirring means and guide grooves used in the developing tank of FIG.

FIG. 4A is an enlarged vertical sectional view of a mode in which jet stirring of a developing tank of the photosensitive material processing apparatus of the present invention is performed from the inside of the photosensitive material, and FIG. FIG. 4 shows a side view of a transport path for guided film.

FIG. 5 (a) shows a linear expansion coefficient of 5.3 × 10 ⁻⁵ cm / cm.
C represents the infrared absorption spectrum of PS modified PPE at
(B) PS having a linear expansion coefficient of 7.5 × 10 ⁻⁵ cm / cm ° C.
4 shows an infrared absorption spectrum of a modified PPE.

FIG. 6 is a graph showing changes in tensile strength, elongation, flexural strength, and flexural modulus of a guide member in an immersion test.

[Explanation of symbols]

 20 Developing tank 33A Guide groove (guide)

Continuation of front page (56) References JP-A-1-140149 (JP, A) JP-A-3-209245 (JP, A) JP-A-5-34890 (JP, A) JP-A-1-129253 (JP) JP-A-62-79462 (JP, A) JP-A-4-42648 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03D 3/08 G03C 5/29

Claims (3)

(57) [Claims] 1. A step of processing a silver halide photographic light-sensitive material under conditions in which at least one processing solution has a temperature of 40 ° C. or more and 50 ° C. or less, and contains a developing agent having a concentration of 15 mmol / L or more and 60 mmol / L or less. Developing the silver halide photographic light-sensitive material, and transporting the silver halide photographic material along a guide installed along the transport direction to support both ends of the photosensitive material. The member constituting the guide has a linear expansion coefficient of 6 × 10 ⁻⁵ (c
m / cm ° C) or less, -1.0 × 10 ^-5 (cm / cm ° C)
And the inner width of the groove of the guide is 0.5 mm
Not less than 5.0 mm and groove depth is not less than 2 mm and 5 mm
A method for processing a silver halide photographic light-sensitive material, which is as follows. 2. An automatic silver halide photographic light-sensitive material transporting apparatus comprising a processing tank for processing a silver halide photographic light-sensitive material and a transport means for transporting the photosensitive material through a predetermined path in the processing tank. A guide is provided along a conveying direction to support both ends of the photosensitive material in a conveying path of the photosensitive material, and a member constituting the guide has a linear expansion coefficient of 6 × 10 ⁻⁵ (c
m / cm ° C) or less, -1.0 × 10 ^-5 (cm / cm ° C)
Wherein the inner width of the groove of the guide is 0.5 mm or more and 5.0 mm or less, and the groove depth is 2 mm or more and 5 mm or less. apparatus. 3. The halogenation according to claim 2, wherein the member constituting the guide contains a polymer compound formed of a polymer containing a repeating unit represented by the following general formula (I). Processing equipment for silver photographic materials. Embedded image In the formula, R represents an alkyl group, and n is 10 to 100000
Represents an integer of 0.