JP2006023723A - Development processing apparatus for silver halide color paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing apparatus for a silver halide color paper, the apparatus (a) which is capable of rapid processing so that a finished print can be handed over a customer on the spot, (b) which requires a small installation area suitable for a minilab, (c) which ensures stability of a processing liquid with less deterioration of the processing liquid even during a non-busy season, and (d) which constantly maintains normal image quality. <P>SOLUTION: The development processing apparatus for a silver halide color paper includes: respective processing tanks for processing with a color developing solution followed by a bleaching solution and successively with a solution having fixing ability; and a liquid-tight sealed passage for a light-sensitive material between the processing tank of the bleaching solution and the processing tank of the liquid having fixing ability so as to make a light-sensitive material pass through. The light-sensitive material is conveyed in a solution through the passage between processing tanks. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a development processing apparatus for silver halide color paper (hereinafter sometimes simply referred to as color paper), and in particular, maintains the finish quality of prints obtained by processing color paper and the suitability of photographic processing solutions. The present invention relates to a space-saving development processing apparatus that can be processed for a short time as it is.

In recent years, a business form in which an automatic development processing device called a minilab that processes photographic photosensitive materials is installed at the photographic store front instead of collecting and delivering between the photographic store and the processing laboratory for quick service to general users, etc. is doing. Minilabs are demanding rapid finishing so that customers who have already taken the photographic material can deliver the finished print on the spot without having to revisit it. In particular, the photography media for which color prints are requested in recent years include not only silver halide photographic film but also electronic image recording media taken with a digital camera, so that it is easy and fast to get used to new customers. A service to provide is needed.
Color copying methods such as ink-jet method, dye thermal transfer method, and color electrophotographic method are suitable for giving a "easy and fast" feeling, but these images are satisfied because they do not have pictorial image quality. Customers are limited.
The thermal development color diffusion transfer method (trade name Pictrocolor) has been proposed as a minilab print creation means that achieves both image quality and ease and speed. For example, Non-Patent Document 1 describes the image forming materials and printer technology. Has been done. However, this method is disadvantageous in that it produces an unwanted product called a donor film that must be discarded.

  On the other hand, an apparatus has been devised that uses color paper, which is excellent in terms of quality, and performs the processing simply and quickly. For example, in Patent Document 1, a photosensitive material conveyance path between processing tanks for development, bleach-fixing, rinsing, and the like is coupled with a minute gap and a liquid leakage prevention nozzle to shorten the time during which the photosensitive material is conveyed outside the tank. A method has been disclosed, and it has been shown that a photosensitive material containing a specific magenta coupler can be processed in a minimum of 63 seconds. Further, Patent Document 2 discloses a rapid processing apparatus in which a liquid leakage prevention nozzle is provided between the processing tanks of the photosensitive material conveyance path and directly connected to each other, and each tank is arranged up and down to achieve further space saving. Is disclosed. However, the method of Patent Document 1 is limited in the photosensitive material that can be applied, and it is considered that there is a restriction in the maintenance of a nozzle that is in gas phase contact with a structure in which a minute gap is provided between tanks. However, this method also requires liquid level control of the tank in contact with the gas phase. However, although these are also problems to be solved, the more essential problem is that the color paper processing by either device of Patent Documents 1 and 2 can be speeded up, and the finished print can be handed over on the spot without visiting the customer again. It is still not enough for a quick finish.

  As can be seen from the above prior art, no satisfactory means has yet been found in order to meet the needs of recent minilab customers in terms of both pictorial image quality and rapid processing.

The above-mentioned prior art relating to the invention of this application includes the following documents.
JP-A-7-234488 JP-A-6-130617 Kosugi, “Heat Development Diffusion Transfer Type Color Printer”; Journal of the Japan Photography Society, 64 (5), 292-296 (2002)

The present invention has been made from the above background, and its purpose is to provide a processing apparatus for silver halide color paper that gives the customer visiting the minilab both the image quality of the finished print and the “easy and fast” feeling. It is to provide.
Specifically, (a) it is possible to quickly process finished prints to customers on the spot, (b) only a small installation area suitable for minilabs, and (c) deterioration of the processing liquid even in low seasons. It is an object of the present invention to provide a processing apparatus for silver halide color paper that can ensure a small processing solution stability and (d) always maintains a normal image quality.

The present inventor has intensively studied a development processing apparatus that satisfies the above-mentioned problems, and combines a specific processing step, a specific photosensitive material transport method, and a processing apparatus that embodies a transport mechanism that enables the transport. I found that the problem could be solved.
That is, the above object is achieved by the present invention having the following configuration.

(1) In a development processing apparatus for silver halide color paper, each processing tank for processing with a bleaching solution following a color developer processing and subsequently processing with a solution having a fixing ability is provided. A photosensitive material passage is provided between the processing bath and a processing bath for a solution having a fixing ability so that the photosensitive material can be liquid-tightly sealed so that the photosensitive material is conveyed in the liquid through the passage between the processing baths. Development processing equipment for silver halide color paper.
(2) The developing apparatus for silver halide color paper according to (1), wherein the processing tank for the bleaching solution and the processing tank for the liquid having fixing ability are arranged in a vertical relationship.
(3) The development for silver halide color paper as described in (1) or (2) above, wherein the total processing time of the bleaching solution and the fixing solution is 12 seconds or less. Processing equipment.
(4) The development processing apparatus for silver halide color paper as described in (3) above, wherein the total processing time of the bleaching solution and the fixing solution is 10 seconds or less.
(5) Processing baths for all immersion processes from color developer processing to rinsing (or rinsing) processing have photosensitive material passages that are liquid-tightly sealed so that photosensitive materials can pass between adjacent processing baths. The development processing apparatus for silver halide color paper according to any one of (1) to (4) above, wherein the photosensitive material is conveyed between the processing tanks in a liquid.

The processing apparatus of the present invention is characterized in that, in terms of processing steps, bleaching is carried out after color development, followed by processing with a processing solution having a fixing ability (fixing solution or bleach-fixing solution), that is, bleaching. This is a processing step (also called separate type bleach-fixing) that is performed by separating the liquid processing and the fixing solution (or bleach-fixing solution) processing. In terms of the method of transporting the photosensitive material, processing of the bleaching solution and the solution having fixing ability A structure in which a photosensitive material passage that is liquid-tightly sealed so that the photosensitive material can pass between the tanks is provided and the photosensitive material is transported in the liquid between the processing tanks, and the above-described processing steps and a transport system are possible. The processing apparatus has a transport mechanism.
With this feature, the apparatus of the present invention can exhibit various effects as described in the next section.

  A structure and a transport mechanism that separates the bleaching solution processing and the fixing solution processing, and transports the photosensitive material in the liquid through a passage in which the photosensitive material is hermetically sealed so that the photosensitive material can pass between the processing bath of the bleaching solution and the fixing solution The silver halide color paper processing apparatus of the present invention has (a) a rapid processing that can hand-over the finished print to the customer on the spot, and (b) the processing apparatus can be miniaturized, As a result, only a small installation area that can cope with the limited size of the minilab is required. (C) Since there are few openings in the processing apparatus having fixing ability, air oxidation is suppressed and contamination of the processing liquid is required. Therefore, the stability of the processing solution can be ensured even in the quiet period, and (d) normal image quality is always maintained.

Hereinafter, the processing apparatus of the present invention will be described in more detail.
In terms of processing steps, the processing apparatus of the present invention is an apparatus applied to a step of performing a bleaching process subsequent to color development and then processing with a processing solution having a fixing ability (fixing solution or bleach-fixing solution). . This process is a separate bleach-fixing type processing step in which the bleaching solution processing and the fixing solution processing are separated. In terms of the method of transporting the photosensitive material, a photosensitive material passage is provided between the processing baths of the bleaching solution and the solution having fixing ability so that the photosensitive material is sealed in a liquid-tight manner so that the photosensitive material can pass therethrough. It is a device that adopts the method.
That is, the processing apparatus of the present invention is a processing apparatus having a structure and a transport mechanism that enable the above-described processing steps and transport system.
Here, “liquid-tight” means that the photosensitive material does not come into contact with air.

In particular, in the processing apparatus of the present invention, the processing bath for the bleaching solution and the processing bath for the liquid having fixing ability are arranged in an upper and lower positional relationship (the processing bath for bleaching liquid is placed on the processing tank for fixing solution). Accordingly, it is advantageous that a functional arrangement that embodies the above-described process and transport method can be performed and that the floor area can be further reduced.
A typical embodiment of such a development processing apparatus of the present invention will be described below with reference to FIGS. In the following drawings, members are represented by member numbers, and treatment tanks and treatment liquids are designated by their respective names. However, common members, treatment tanks, treatment liquids, etc. have common member numbers, treatment tank names, and treatment liquids. The name such as.

  In a typical embodiment of the development processing apparatus of the present invention shown in FIG. 1, a color developing tank 1 containing a color developing solution labeled CD, a bleaching tank 2 containing a bleaching solution labeled Bleach, and a Fix The fixing tank 3 containing the prepared fixing liquid, and the six rinsing tanks 4a to 4f containing the first to sixth rinsing liquids labeled Ps-1 to Ps-6 sent in a countercurrent cascade system are shown in the figure. In the color developing tank 1, the bleaching tank 2, the fixing tank 3, and the sixth rinsing tank 4f, the color developing replenishing solution and the bleaching replenishing solution are indicated as indicated by the framed characters. The fixing replenisher and the rinse replenisher are respectively replenished.

  In the color developing tank 1, the bleaching tank 2h, the fixing tank 3 and the first rinsing tank 4a, CDO. F. , BleachO. F. , FixO. F. PS-10. F. As described above, there is provided a discharging means for discharging the overflow (OF) of each processing solution from the processing tank. When the rinse replenisher indicated as PS replenishment in the figure is replenished to the sixth rinse tank 4f, the rinse liquid PS-6 in the sixth rinse tank 4f which becomes excessive by replenishment is transferred to the fifth rinse tank 4e. Is done. In this way, the liquid is transferred from the sixth rinsing tank 4f to the first rinsing tank 4a while performing the rinsing process in the countercurrent cascade system indicated by the dotted arrow, and reaches the first rinsing tank 4a to the rinse overflow PS. -10. F. As discharged.

The photosensitive material indicated by the framed characters enters the color developing tank 1 in accordance with the photosensitive material conveying path indicated by the solid line, and is guided to the bleaching tank 2 by the aerial conveying path 5 after the color development processing, where the bleaching process is performed. Subsequently, it is conveyed to the fixing tank 3 through the submerged conveyance path 6 that is liquid-tightly sealed by a single blade 10 provided between the bleaching tank 2 and the fixing tank 3 and capable of passing a photosensitive material. The photosensitive material that has undergone the fixing process in the fixing tank 3 passes through the submerged conveyance path 7 sealed by the single blade 11 so that the photosensitive material can pass between the fixing tank 3 and the first rinsing tank 4a. It is conveyed to the tank 4a. The photosensitive material is rinsed in the first rinsing tank 4a, and then passes through the submerged conveyance path 8a sealed by the single blade 12 so that the photosensitive material can pass between the first rinsing tank 4a and the second rinsing tank 4b. It is conveyed to the 2nd rinse tank 4b, and a rinse process is performed here continuously. In the same manner, while further rinsing is performed, the second rinsing tank 4b is transferred to the sixth rinsing tank 4f through the submerged transfer paths 8b to 8e sealed by the blades 13 to 16, and the sixth rinsing tank 4f is transferred. The whole dipping process is finished and transferred to a drying process (not shown) and dried to obtain a finished color photograph (usually a color print).

  Unlike the single blades 10 to 12, the blades 13 to 16 are double blades. The details will be described later with reference to FIGS. 5, 6, and 7, but the degree of liquid tightness is increased by the double blade, and the amount of liquid transferred from the upstream tank to the downstream liquid can be reduced. . In the present specification, the “photosensitive material passage sealed in a liquid-tight manner so that the photosensitive material can pass through” as described above allows a slight amount of liquid transfer through the gap between the sealing portions by a blade or a shielding means having an equivalent function. This means a passage with a degree of shielding. In other words, if the upstream hydraulic pressure of the blade is higher than the downstream hydraulic pressure, the liquid can be moved according to the differential pressure, but if the upstream and downstream hydraulic pressures are equal, the photosensitive material (web) passes. In addition, the passage of the liquid passing through the seal portion gap is not allowed. During the rest of the processing apparatus, the slit provided in the tank wall that becomes the photosensitive material passage is shielded by the opposing blades that are in contact with each other or by the single-sided blade and the tank wall surface of the slit part, and there is no movement of the liquid. .

  Although not shown in FIG. 1, suitable transport means, for example, a transport roller, a driving roller such as a nip roller, a counter free roller, and a staggered array free roller can be provided in the submerged transport path.

  In FIG. 1, the cascading rinse liquid transfer between the tanks indicated by the dotted line arrow is, for example, a counter-flow tank in which a minute liquid passage hole is provided between the tanks so that mixing of the liquid is negligible. It can be carried out by means of interphase transfer.

FIG. 2 shows another exemplary embodiment of the development processing apparatus of the present invention.
In the development processing apparatus shown in FIG. 2, the color developing tank 21 containing the color developer indicated as CD is divided into two tanks 21a, 21b and two tanks via a submerged transport path 25a sealed liquid-tightly by a single blade 29a. In addition, a submerged transport path 25b is formed between the color developing tank 21b and the bleaching tank 22 and sealed with a single blade 29b. Along with the vertical arrangement of the color developing tanks 21a and 21b, the bleaching tank 22, and the fixing tank 23, the first rinse tank 24a is disposed below the second rinse tank 24b and the first rinse tank 24a to the sixth rinse tank 24f. Are arranged in a vertical positional relationship. Further, single blades are used as the blades 24a to 24f in the photosensitive material passages between the respective rinse tanks. Others are the same as those described in FIG. Even if the member numbers of the respective constituent members are different from the corresponding constituent member numbers in FIG. 1, the corresponding members are members having the same function, and thus description thereof is omitted. Further, the processing flow of the photosensitive material, the addition of the replenisher, and the discharge of the overflow are the same as those described for the development processing apparatus in FIG.

  In the apparatus of this embodiment, the color developing tank and the bleaching tank are not transported in the air but directly connected by a passage sealed by a blade, thereby suppressing air oxidation, shortening the processing time, and installing the processing apparatus. 1 is superior to the apparatus shown in FIG. 1, but both apparatuses satisfy the requirements defined in the present invention, and the following detailed description includes these apparatuses. It applies to everything.

Next, a description will be given of a blade for providing a submerged passage for the photosensitive material between the processing tanks. The blade is attached to the passage so that the tip portions of the blade come into contact with each other when the photosensitive material does not pass. When the photosensitive material passes, the front end portion is expanded by the entry of the photosensitive material. This blade preferably has a base attached to the passage and a free end (sometimes referred to as a tip) whose thickness gradually decreases toward the tip, but the thickness is almost the same from the base to the tip. It may be a thing. In general, the average inclination angle of the blade with respect to the surface of the photosensitive material is preferably about 10 to 70 °, and more preferably about 20 to 45 °. Further, the length from the base of the blade to the tip is preferably 10 to 50 mm, and particularly preferably 15 to 25 mm. The length of the overlapping portion of the blade tip portions when the light-sensitive material does not pass through the pair of blades installed facing each other is preferably about 1 to 10 mm, particularly about 2 to 5 mm. By setting it as such conditions, the adhesiveness of the front-end | tip part of a braid | blade at the time of the non-passing of a photosensitive material is ensured, and the distribution | circulation of each process liquid can be interrupted | blocked effectively. In addition, the flow of each processing solution during passage of the photosensitive material can be negligible.

3 to 7 show various aspects of the blade applied for this purpose, but the present invention does not restrict the use of other blades or sealing means having equivalent functions.
FIG. 3 is a cross-sectional view of the submerged conveyance path showing a state in which a pair of single blades is provided on the wall of the processing tank to form a submerged conveyance path for the photosensitive material. In FIG. 3, on the tank wall 32 of the processing tank, the photosensitive material can move from the processing tank on the upstream side (left side of the tank wall 32) to the processing tank on the downstream side (right side of the tank wall 32) according to the conveying direction indicated by the arrow. A slit 33 is provided. In addition, the upstream tank side cross section of the tank wall 32 is inclined with respect to the passage so as to open to the upstream side, and a pair of blades 31 are in contact with each other with a free piece on the downstream side, When passing through the photosensitive material, the photosensitive material is fixed so as to be in contact with both sides. In this way, the free means of the pair of blades 31 are in contact with each other directly or with the photosensitive material (or the conveyor belt) in between, so that the sealing means 30 for cutting off the contact between the processing liquid in the upstream tank and the downstream processing liquid is provided. Forming.

  Therefore, the transfer of the processing liquid in the upstream tank to the downstream side is suppressed by the sealing means 30 during the suspension of the development processing apparatus. During operation of the processing apparatus, the photosensitive material passes through between the free ends facing each other with the upstream processing solution occluded in the photosensitive layer, thereby causing contamination of the upstream processing solution to the downstream processing solution. Is caused. However, the degree of contamination is such that the effect of the present invention can be maintained, and a sealing method using a blade is preferable as a sealing means embodying the present invention.

  FIG. 4 is a cross-sectional view of the submerged conveyance path showing another embodiment of the sealing means. The single blade 31 is used as in FIG. 3, but the blades do not form a pair, and on one side of the photosensitive material path, One surface of the photosensitive material (or guide film) is in contact with the tank wall 32, and the other surface is in contact with the free end of the blade 31, and this structure forms a sealing means. The slit end on the downstream side of the tank wall 32 on the side in contact with the photosensitive material (or the guide film) is provided with a roundness 32a so that the photosensitive material is not scratched.

  FIG. 5 is a cross-sectional view of the submerged conveyance path showing a mode in which double blades 31 a and 31 b are used as the sealing means 30. The tank wall 34 is provided with two inclined surfaces with respect to the photosensitive material passage in the positional relationship shown in the figure, and each pair of the double blades 31a and 31b has a free piece on the downstream side, and the upper and lower sides of the photosensitive material. It is fixed so that it touches. Accordingly, the first seal in which the pair of free pieces of the blade 31a and the photosensitive material seal the processing solution in the upstream tank, and the processing solution in which the free piece of the pair of blades 31b and the photosensitive material have passed the first seal. A sealing means 30 having a two-stage configuration of a second seal that seals from the processing liquid in the downstream tank is formed.

FIG. 6 is a cross-sectional view of the submerged conveyance passage showing a mode of the sealing means different from that in FIG. 5, although the double blades 31 a and 31 b are used as the sealing means 30. The tank wall 35 is provided with two oblique surfaces with respect to the photosensitive material passage in the illustrated positional relationship, and the double blades 31a and 31b are fixed with their free pieces downstream. Similar to the sealing means of FIG. 5, the tank wall 35 is provided with a small hole 37 so that the processing liquid confined between the first seal and the second seal can be returned to the upstream tank. . Therefore, when the water pressure at the intermediate portion between the first seal and the second seal becomes high, the processing liquid at the intermediate portion returns to the upstream side to suppress downstream contamination.
Other functions are the same as those described for the double-blade type seal portion shown in FIG.

FIG. 7 is functionally different from FIG. 6 in that it has a function of adjusting the liquid pressure of the processing liquid confined between the first seal and the second seal in the sealing means 30 using the double blades 31a and 31b. In the sealing method of FIG. 7, a small hole 36 is provided in the first double blade 31a so that the processing liquid confined between the first seal and the second seal can be returned to the upstream tank. It has been. Therefore, as in the sealing means of FIG. 6, when the water pressure at the intermediate portion between the first seal and the second seal becomes high, the intermediate processing liquid returns to the upstream side to suppress downstream contamination.
Other functions are the same as those described for the double-blade type seal portion shown in FIG.

  The blade material may be any material as long as it does not adversely affect each processing solution. For example, natural rubber, chloroprene rubber, nitrile rubber, butyl rubber, fluorine rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, ethylene propylene rubber, silicon rubber And various elastic materials such as polyurethane, soft polyvinyl chloride, polyethylene, polypropylene, ionomer resin, fluorine resin, silicone resin and the like. In particular, polyurethane is preferable from the viewpoint of durability and liquid leakage.

  The adhesion force between the blades is given by the elastic force of the blades, but a magnetic material is blended in the tip part of the blade (such as a rubber magnet), and the tip parts are attracted to give the adhesion force. It is also possible to increase it. In addition, even if the photosensitive material slides on the blade, there is almost no adverse effect such as scratches on the emulsion surface, but if this is not negligible, or if the sliding resistance is to be reduced, the inner surface of the blade A smoothing treatment may be applied, or a surface treatment such as coating the inner surface with a lubricant such as silicone or Teflon may be used.

  The linear speed of conveyance of the color paper developing apparatus of the present invention is preferably 100 mm / second or less. More preferably, it is 20 mm / second to 80 mm / second, and particularly preferably 25 mm / second to 60 mm / second.

The color paper development processing apparatus is transported by a method in which the color paper is cut to the final size before development processing (sheet type conveyance method), or a method in which the development processing is performed in a long roll and then cut to the final size after processing (cine). Mold conveyance system). The cine type conveyance method is preferably a sheet type conveyance method because a photosensitive material of about 2 mm is wasted between images.
The color paper applied to the development processing apparatus of the present invention may be a sheet or a roll. In the processing of photosensitive material in the development processing device, the roller transport method is used in the device that processes sheet-like color paper, and in the device that processes roll-shaped paper, the roller transport method, belt transport, and a leader is bonded to the roll tip. Any known method such as a reader transport method may be used.

Various component materials are used in the development processing apparatus, and preferable materials are described below.
Tank materials such as treatment tanks and temperature control tanks are modified PPO (modified polyphenylene oxide),
Modified PPE (modified polyphenylene ether) resin is preferred. Examples of the modified PPO include “Noryl” manufactured by GE Plastics, and the modified PPE includes “Zylon” manufactured by Asahi Kasei Kogyo, “Iupiace” manufactured by Mitsubishi Gas Chemical, and the like. Moreover, these materials are suitable for parts that may come into contact with the processing liquid such as processing racks and crossovers.

The roller material of the processing part is PVC (polyvinyl chloride), PP (polypropylene), P
Resins such as E (polyethylene) and TPX (polymethylpentene) are suitable. These materials can also be used for other processing liquid contact portions. In addition, PE resin is preferable also for the material of the replenishment tank by blow formation.
Materials for processing parts, gears, sprockets, bearings, etc. include PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (fully aromatic polyester resin, liquid crystal polymer) ) Etc. are suitable.
PA resin is polyamide resin such as 66 nylon, 12 nylon, and 6 nylon, and those containing glass fiber or carbon fiber are strong against swelling by the treatment liquid and can be used.

High molecular weight products such as MC nylon and compression molded products can be used without fiber reinforcement. UHMPE resin is suitable for unreinforced products such as “Lubema” manufactured by Mitsui Petrochemical Co., Ltd., “Hi-X Million” Sakuhin Kogyo Co., Ltd. “New Light”, Asahi Kasei Kogyo Co., Ltd. “Sun Fine”, etc. Is suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000.
The PPS resin is preferably glass fiber or carbon fiber reinforced. Examples of the LCP resin include ICI Japan Co., Ltd. “Victrex”, Sumitomo Chemical Co., Ltd. “Econol”, Nippon Oil Co., Ltd. “Zyder”, Polyplastics Co., Ltd. “Vectra”.
In the case of an apparatus using a conveyor belt, the material is preferably ultrahigh strength polyethylene fiber or polyvinylidene fluoride resin described in Japanese Patent Application No. 2-276886.
In the case of an apparatus using a squeeze roller or the like, a foamed vinyl chloride resin, a foamed silicon resin, or a foamed urethane resin is suitable as the soft material. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd.
EPDM rubber, silicon rubber, Viton rubber and the like are preferable as rubber materials such as a pipe joint, an agitation jet pipe joint, and a sealing material.

  In the development processing apparatus of the present invention, the characteristic of the processing step is a step of performing a bleaching process subsequent to color development and then processing with a processing solution having a fixing ability (fixing solution or bleach-fixing solution). Processing that separates bleaching solution processing and fixing solution processing (also called separate type bleaching / fixing) is applied to photographic materials such as color negative films, and also uses red blood salt bleaching solution. Although it was used for color paper processing before 1971, the color paper processing after 1971 in which the ethylenediaminetetraacetic acid iron complex bleaching agent was used was replaced with bleach-fixing processing. Processing is now obsolete. However, in the present invention, when separate bleaching / fixing that is not currently used for developing color paper in the world market is applied to silver chloride color paper, processing fatigue is extremely high in both the bleaching solution and the fixing solution. It was found that not only the bleaching time and the fixing time can be remarkably shortened, but also that the processing solution is less fatigued even in the off-season and the development processing operation can be stably operated. In addition, it has been found that the processing apparatus can be reduced in size due to shortening of the processing time, and the processing liquid consumption can be reduced due to low fatigue, and the processing cost can be reduced.

  Furthermore, in ordinary color paper processing, since the photosensitive material that has undergone the color development process moves to the bleach-fixing process while occluding the color developer, the occurrence of bleaching fogging, poor color development (leuco dye failure), tar-like insoluble matter and the occurrence thereof. There are many troubles such as adhesion to photosensitive materials. It has also been found that the occurrence of these failures is suppressed when a separate type bleaching / fixing treatment is performed.

A further advantage of the present invention is that a photosensitive material passage in which the photosensitive material is hermetically sealed so that the photosensitive material can pass therethrough is provided between the bleaching solution and the solution processing tank having fixing ability, and the photosensitive material is conveyed between the processing vessels in the solution. It can be seen that the method used is adopted. In general-purpose development processing equipment for color paper, the photosensitive material is transported between the processing tanks by air transport that is once taken out of the liquid from the preceding processing tank and immersed in the next tank through an air path. However, in the present invention, at least the bleaching solution and the solution having a fixing ability between the treatment tanks can be transported between the processing tank and the processing time can be shortened by eliminating the in-liquid transport and the air time. Can be reduced in size, and the apparatus cost can be reduced. Further, since the opening surface of the processing tank for the liquid having fixing ability can be substantially eliminated, the deterioration of the liquid having fixing ability due to air oxidation or evaporation is suppressed, and the fixing activity is kept stable. This effect can suppress the increase in Dmin (yellow stain) that tends to occur particularly in the off-season and small-scale minilabs, and contributes to stable and improved quality. Furthermore, because of low fatigue, processing liquid consumption can be reduced and processing costs can be reduced. In the present invention, these advantages are further exhibited in addition to the effects of the separate processing.
Japanese Patent Application Laid-Open No. 7-234488 discloses a development processing apparatus having a photosensitive material passage shielded by a blade. However, the photosensitive material passage of this apparatus is not liquid-tight because it has an air contact portion. Then, the effect of the present invention is not recognized.

  Due to the rapid processing effect of both the separation type processing method of the bleaching solution and the fixing solution of the development processing apparatus of the present invention described above and the conveyance method through the photosensitive material passage in which the two tanks are sealed in a liquid-tight manner, the present invention. Then, the total processing time of the processing of the bleaching solution and the processing of the solution having fixing ability can be 12 seconds or less, and can be 10 seconds or less, preferably 6 seconds or less. The processing time shortening limit seems to be about 2 seconds for both the bleaching time and the fixing time. However, the processing has been sufficiently desilvered through the separate type bleaching and fixing process and the liquid-tight immersion passage of the present invention. As long as this is the case, the short time side of the processing time is not limited.

Next, a color processing process to which the processing apparatus of the present invention is applied will be described.
The color development processing to which the bleaching concentrated composition of the present invention is applied comprises a color development step, a bleaching step, a fixing step, a rinsing or washing step and a drying step. The processing solution in the fixing step is a bleach-fixing solution in addition to the fixing solution. A processing solution having a fixing ability such as the above may be used. As described above, the photosensitive material passage is sealed in a liquid-tight manner so that the photosensitive material can pass between the bleaching step and the fixing step, and the photosensitive material is conveyed in the liquid through the passage between the processing tanks. The photosensitive material conveyance path in between is not limited to the submerged conveyance type, but may be an air conveyance method requiring air time. Preferably, the photosensitive material passage in the entire immersion process from entering the color developer to finishing the final rinse is the submerged passage.
Auxiliary processes such as an intermediate rinse process, an intermediate water washing process, and a neutralization process may be inserted between the immersion processes. In addition to the rinsing or rinsing step, an image stabilizing bath for the purpose of image stabilization can be provided between the rinsing or rinsing step and the drying step.

The replenishment amount of the color developer is preferably 10 to 200 ml, more preferably 15 to 150 ml, and most preferably 20 to 90 ml per 1 m ² of the photosensitive material.
The replenishing amount of the bleaching solution and the fixing solution can be reduced, and is preferably 5 to 30 ml, more preferably 5 to ²⁰ ml, and most preferably 5 to 15 ml per 1 m ^{2 of the} photosensitive material. Further, the replenishment amount of the rinsing liquid or the washing water to the rinsing tank is preferably 50 ml to 200 ml in the entire rinsing liquid, preferably in the case of a rinsing tank having a multi-tank configuration as shown in FIGS. 1 and 2. A method in which the above tank is replenished with the above amount and overflowed from the first rinsing tank in a countercurrent cascade system is suitable.

  Here, the color development time is preferably 200 seconds or shorter, more preferably 120 seconds or shorter, still more preferably 80 seconds or shorter and 6 seconds or longer. Similarly, the bleaching time is preferably 100 seconds or less, more preferably 30 seconds or less, still more preferably 15 seconds or less, even more preferably 10 seconds or less, and particularly preferably 8 seconds or less and 2 seconds or more. The fixing time is preferably 150 seconds or less, more preferably 60 seconds or less, still more preferably 40 seconds or less, even more preferably 30 seconds or less, still more preferably 20 seconds or less, and even more preferably 10 seconds or less and 2 seconds or more. . As described above, the total of the bleaching time and the fixing time is preferably 12 seconds or shorter, more preferably 10 seconds or shorter, and particularly preferably 6 seconds or shorter and 2 seconds or longer. In addition, the rinsing or rinsing time is preferably 90 seconds or shorter, more preferably 60 seconds or shorter, even more preferably 30 seconds or shorter and 3 seconds or longer, including the case of a multi-tank configuration.

  The processing solution temperature in the color development step, bleaching step, fixing step and rinsing step is generally 30 to 40 ° C., but it is also possible to perform high temperature rapid processing at 38 to 60 ° C., more preferably 40 to 50 ° C. It is one aspect | mode.

  In addition, the processing time of each process means the time from when the photosensitive material is immersed in the processing liquid of the said process to being immersed in the processing liquid of the next processing process. When processed with an ordinary automatic processor, the photosensitive material is immersed in the processing solution in the processing step and the processing tank is transported through the air toward the processing solution in the next processing step. The processing time is defined as the total of both of the measured time (so-called air time and air time). In the development processing apparatus of the present invention, the immersion time and the processing time in the bleaching step are the same. The rinsing or rinsing time refers to the time from when the photosensitive material enters the rinsing tank or rinsing tank until the drying process begins.

The amount of rinsing solution can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as coupler) and application, the temperature of the rinsing solution (washing water), the number of rinsing solutions (washing tank) (stage number), and various other conditions. Can do. Of these, the relationship between the number of rinsing liquid tanks (flush tanks) and the amount of water in the multi-stage counter-current system is the Journal of the Society of Motion Picture and Motion of Picture Picture and Television Engineers) Vol. 64, p. It can be determined by the method described in 248-253 (May 1955).
Usually, the number of stages in the multistage countercurrent system is preferably from 3 to 10, particularly from 3 to 5.

  According to the multi-stage counter-current system, the amount of the rinse liquid can be greatly reduced, and the increase of the residence time of water in the tank causes problems such as bacteria breeding and the generated suspended matter adhering to the photosensitive material. As a solution, a rinsing solution containing an antibacterial and antifungal agent described later is preferable.

  Then, post-processing such as a drying process is performed on the color paper that has been subjected to development processing. In the drying process, drying can be accelerated by absorbing moisture with a squeeze roller or cloth immediately after the development process (rinsing process) from the viewpoint of reducing the amount of moisture carried into the image film of the color paper. is there. Of course, drying can be accelerated by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the photosensitive material or by the method of removing the exhaust air.

Next, a processing solution applied to the development processing apparatus of the present invention will be described. First, a color developing solution used for color development will be described.
In this specification, unless there is a special meaning to distinguish between the tank liquid in the processing tank and the replenisher added to the processing tank in each step, the processing liquid (for example, the color developing replenisher and the color developing replenisher are combined). Included in the liquid).

The color developer contains a color developing agent.
Preferred examples of the color developing agent include known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4- Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N— Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N- (Β-Methanesulfonamidoethyl) aniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-3-methyl-N-ethyl-N- (β-methoxy Til) aniline 11) 4-amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-amino-3-methyl-N- (3-carbamoylpropyl-Nn-propyl- Aniline 13) 4-amino-N- (4-carbamoylbutyl-Nn-propyl-3-methylaniline 15) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 16) N- (4 -Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide

Of the above p-phenylenediamine derivatives, exemplary compounds 5), 6), 7), 8) and 12) are particularly preferred, and among them, compounds 5) and 8) are preferred. Moreover, these p-phenylenediamine derivatives are usually in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate in the state of a solid material.
The content of the aromatic primary amine developing agent in the processing agent is such that the concentration of the developing agent in the color developing solution is 2 to 200 mmol, preferably 6 to 100 mmol, more preferably 10 mmol, per liter of the developing solution. Added to ˜40 mmol.

  An organic preservative may be added to the color developer as a preservative. Organic preservatives refer to all organic compounds that reduce the degradation rate of an aromatic primary amine color developing agent by being included in a color developer. That is, it is an organic compound having a function of preventing air oxidation of a color developing agent, among others, hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, Saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines are particularly effective organic preservatives. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP 52-143020, JP 48-30496 It is disclosed in each gazette or specification such as No ..

Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, and JP-A-54-3532. The alkanolamines described herein, polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, and the like may be contained as necessary. In particular, alkanolamines such as triethanolamine and triisopropanolamine, substituted or unsubstituted dialkylhydroxylamines such as disulfoethylhydroxylamine, diethylhydroxylamine, or aromatic polyhydroxy compounds may be added. .
Among the organic preservatives, details of the hydroxylamine derivative are described in JP-A Nos. 1-97953, 1-186939, 1-186940, 1-187557 and the like. In particular, adding both a hydroxylamine derivative and amines may be effective in improving the stability of the color developer and improving the stability during continuous processing.
Examples of the amines include cyclic amines as described in JP-A-63-239447, amines as described in JP-A-63-128340, and other JP-A-1-86939. Examples thereof include amines described in JP-A-1-187557. Although the content of the preservative in the processing agent varies depending on the type of the preservative, it is generally added so that the concentration in the working solution is 1 to 200 mmol, preferably 10 to 100 mmol, per liter of the developing solution. It is done.

If necessary, chlorine ions may be added to the color developer for color paper. The color developer usually contains chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / L in many cases, but chlorine ions are usually released as a by-product of development into the developer so that it can be replenished. In many cases, the developer does not need to be added.

Since the light-sensitive material targeted by the present invention is color paper, the color developer does not need to contain bromine ions, but may contain 1.0 × 10 ⁻³ mol / L or less bromine ions.

  When chlorine ions are used as an additive component in the color developer, examples of the chlorine ion supply substances include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride and calcium chloride. Preferred are sodium chloride and potassium chloride.

  The pH of the color developer is preferably 9.0 to 12.0, the pH of the color developer replenisher is preferably 9.0 to 13.5, and the pH of the color developer is 9.0 to 10.5. The pH of the replenisher is more preferably 9.0 to 12.0. Therefore, the color developer and the color developer replenisher can contain an alkali agent, a buffer agent and, if necessary, an acid agent so that the pH value can be maintained.

  In order to maintain the pH when the color developer is prepared, various buffers are preferably used. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent buffering ability in the high pH range of pH 9.0 or higher, and adverse effects on photographic performance even when added to color developers (fogging, etc.) It is particularly preferable to use these buffering agents.

Specific examples of these buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.
Since the buffer is not a component that is reacted and consumed, the concentration in the composition is 0.01 to 2 mol, preferably 0.1 to 0.5 mol, per liter of the color developer. Is decided.

Various color developing solution components, for example, calcium or magnesium precipitation inhibitors, or various chelating agents that are also color developer stability improving agents can be added to the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsiloxanediaminetetraacetic acid, 1 , 2-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2 -Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, 1,2- And dihydroxybenzene-4,6-disulfonic acid It is.
These chelating agents may be used in combination of two or more as required.
The amount of these chelating agents may be an amount sufficient to sequester metal ions in the color developer. For example, it is added so as to be about 0.1 to 10 g per liter.

  If necessary, an arbitrary development accelerator can be added to the color developer used in the present invention. Examples of the development accelerator include thioether compounds described in JP-B-37-16088, p-phenylenediamine compounds described in JP-A-52-49829, JP-A-50-137726, and the like. A quaternary ammonium salt described in US Pat. No. 2,494,903, an amine compound, a polyalkylene oxide described in JP-B-42-25201, and other 1-phenyl-3-pyrazolidones or imidazoles. It can be added as necessary. The added amount in the composition is determined so that the concentration thereof is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter for both the developer and replenisher prepared from the processing agent. .

An optional antifoggant can be added to the color developer used in the present invention, if necessary, in addition to the halogen ions. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Representative examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.
In addition, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developer as necessary. The addition amount in the composition is determined so that the concentration thereof is 0.0001 to 0.2 mol, preferably 0.001 to 0.05 mol, per liter for both the developer and replenisher prepared from the processing agent. .

  In the present invention, an optical brightener can be used as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available niaminostilbene-based brighteners can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Examples of commercially available compounds are described in, for example, “Dyeing Note” 9th edition (Colored dyeing), pages 165 to 168. Among the compounds described therein, Blankophor BSU liq. And Hakkol BRK are listed. preferable. In the case where a fluorescent whitening agent is contained in the color developer, the concentration in the solution is preferably 0.02 to 1.0 mol / liter.

  As the bleaching agent used in the bleaching solution, any known bleaching agent can be used, and in particular, iron (III) organic complex salts (for example, complex salts of aminopolycarboxylic acids) or citric acid, tartaric acid, malic acid, etc. Organic acids, persulfates, hydrogen peroxide and the like are preferable.

  Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Examples of aminopolycarboxylic acids (or salts thereof) useful for forming iron (III) organic complex salts include biodegradable ethylenediamine disuccinic acid (SS form), N- (2-carboxylate ethyl). ) -L-aspartic acid, beta-alanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodia Examples include acetic acid and glycol ether diamine tetraacetic acid. These compounds may be any of sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodioxy Acetic acid is preferable because its iron (III) complex salt has good photographic properties. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid may be used to form a ferric ion complex salt in a solution. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Of the iron complexes, aminopolycarboxylic acid iron complexes are preferred.

  The concentration of the bleaching agent in the bleaching solution is 0.01 to 1.0 mol / liter, preferably 0.03 to 0.80 mol / liter, more preferably 0.05 to 0.70 mol / liter, more preferably It is determined to be 0.07 to 0.50 mol / liter.

Various known organic acids (for example, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, etc.), organic bases (for example, imidazole, dimethylimidazole, etc.) or 2-picolinic acid And the compounds represented by the general formula (Aa) described in JP-A-9-211819 and the compounds represented by the general formula (Bb) described in the same publication including kojic acid. It is preferable to contain. The amount of these compounds added is determined so that the concentration of the prepared treatment liquid is preferably 0.005 to 3.0 mol, more preferably 0.05 to 1.5 mol per liter.
It is also preferable to add an alkali metal nitrate such as potassium nitrate or sodium nitrate because it has an effect of preventing corrosion of the metal member. The addition amount in this case is determined so that the concentration of the prepared treatment liquid is preferably 0.005 to 3.0 mol, more preferably 0.05 to 1.5 mol per liter.
Furthermore, it is preferable to add an alkali halide such as potassium chloride, potassium bromide, sodium chloride, sodium bromide or the like because it has the effect of increasing the bleaching activity. The addition amount in this case is determined so that the concentration of the prepared treatment liquid is preferably 0.005 to 3.0 mol, more preferably 0.05 to 1.5 mol per liter.

  The pH range of the bleaching solution used in the present invention is preferably 2 to 8, more preferably 3 to 7, and most preferably 4 to 6. If the pH is lower than this, the deterioration of the liquid and the leuco conversion of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering is delayed and stain is likely to occur. In order to adjust the pH, acetic acid, the above-described organic acid, and the above-described alkali potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, or an acidic or alkaline buffer as necessary. An agent or the like can be added.

Next, examples of the processing solution having a fixing ability include a fixing solution and a bleach-fixing solution, which will be described together below. However, since the bleaching solution component in the bleach-fixing solution is described in the section of the bleaching solution, it will not be repeated. The compounds used for the fixing solution components in the fixing solution and the bleach-fixing solution are known fixing chemicals, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylene It is a water-soluble silver halide solubilizer such as thioether compounds such as bisthioglycolic acid and 3,6-dithia-1,8-octanediol and thioureas, and these can be used alone or in combination. can do. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The concentration of the fixing chemical in the fixing solution and the bleach-fixing solution is preferably from 0.3 to 3 mol, more preferably from 0.5 to 2.0 mol, per liter of the prepared solution.

  The pH range of the fixing solution and the bleach-fixing solution used in the present invention is preferably from 3 to 9, and more preferably from 4 to 8. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco conversion of the cyan dye are promoted. On the contrary, if the pH is higher than this, desilvering is delayed and stain is likely to occur. In order to adjust the pH, acetic acid, the above-described organic acid, and the above-described alkali potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, or an acidic or alkaline buffer as necessary. An agent or the like can be added.

  In addition, the fixing solution and the bleach-fixing solution may contain various other fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, and the like. In fixing solutions and bleach-fixing solutions, sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) are used as preservatives. Sulfite ion releasing compounds such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), and arylsulfines such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid It preferably contains an acid or the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.

  As a preservative, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added in addition to the above.

For the rinsing liquid, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, chlorinated fungicides such as isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, JP-A-61-267761 Benzotriazole, copper ion, and other publications described in the gazette, Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal” (1986) Sankyo Publishing, Hygiene Technology Association, “Microbial Decontamination, Sterilization, Antifungal Technology” (1982) The bactericides described in the “Industrial Antibacterial and Antifungal Encyclopedia” (1986) edited by the Industrial Technology Association of Japan and the Japanese Society for Antibacterial and Antifungal Society may be used.
Furthermore, a surfactant can be used as a draining agent, and a chelating agent represented by EDTA can be used as a water softening agent.

[Applicable photosensitive material]
Next, the color photographic light-sensitive material applied to the present invention is color paper, that is, color printing paper for color printing, and this light-sensitive material is provided with at least one light-sensitive layer on a support. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer composed of a plurality of silver halide emulsion layers having substantially different color sensitivities on a support.

  In general, a photosensitive material for color printing uses a reflective support, and is often installed in the order of a red color-sensitive layer, a green color-sensitive layer, and a blue color sensitivity in order from the side far from the support. As the silver halide emulsion, a cubic emulsion of silver chloride or silver chlorobromide grains of high silver chloride is used.

The photosensitive silver halide used for the photosensitive material for color printing is a cubic or tetradecahedral crystal grain having a {100} plane (these grains have rounded vertices and higher order planes). May be an octahedral crystal lattice, and the main plane is preferably composed of tabular grains having an aspect ratio of 2 or more and consisting of {100} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. For tabular grains having a main surface of {100} face or {111} face, reference can be made to columns 33 (P7) to P840 (P8) of JP-A No. 2000-352794. In the present invention, a cube is most preferable. The particle size is preferably 0.5 μm or less, more preferably 0.4 μm or less, in terms of cubic conversion side length.

  As the silver halide emulsion used in the present invention, an emulsion containing silver halide grains having a specific silver halide content is used, and the silver chloride content is 90 mol% or more from the viewpoint of rapid processability. The silver chloride content is preferably 93 mol% or more, more preferably 95 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and has excellent latent image stability. The silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, and more preferably 0.07-0. 40 mol% is most preferred. The silver halide grains of the present invention are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above halogen composition.

  The silver halide emulsion used in the present invention preferably contains iridium. As the iridium compound, a 6-coordination complex having 6 ligands and having iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. As one preferred embodiment of the iridium used in the present invention, a hexacoordinate complex having Ir as a central metal having Cl, Br or I as a ligand is preferred, and Ir comprising all six ligands consisting of Cl, Br or I is preferred. A hexacoordinate complex as a central metal is more preferable. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that a hexacoordinate complex having Ir as a central metal having Cl, Br, or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.

  In the present invention, the above-mentioned iridium complex is added directly to the reaction solution at the time of silver halide grain formation, or added to an aqueous halide solution for forming silver halide grains, or to other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the iridium complex is previously incorporated in the grains and to incorporate them into the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

The optimum amount of these metal complexes may vary depending on the size of the silver halide grains to be contained, but it is preferable to use 5 × 10 ⁻¹⁰ moles to 1 × 10 ⁻⁷ moles per mole of silver during grain formation. More preferably, 2 × 10 ⁻¹⁰ mol to 8 × 10 ⁻⁸ mol, particularly preferably 5 × 10 ⁻¹⁰ mol to 5 × 10 ⁻⁸ mol are used.

  In the present invention, in addition to iridium and rhodium, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.

  In the photosensitive silver halide emulsion used in the present invention, examples of spectral sensitizing dyes used for spectral sensitization in the green and red regions include FM cyclic cyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New York, London] (published in 1964). As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. In particular, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, the strength of adsorption, and the exposure temperature. This is very preferable from the viewpoint of dependency.

  The silver halide emulsion processed by the development processing apparatus of the present invention is preferably subjected to gold sensitization known in the art. For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.

Colloidal gold sulfide can also be used, and its manufacturing method is Research Disclosure (37154), Solid State Ionics (Solid).
State Ionics) 79, 60-66, 1995, Compt. Rend. Hebt. Seances
Acad. Sci. Sect. B, 263, 1328, published in 1966. The Research Disclosure describes a method using a thiocyanate ion in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.

  The above gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using other than gold compounds.

  Next, as a printer for producing a print by development processing using the development processing apparatus of the present invention, a general-purpose printer is used, but in addition to being used for a printing system using a normal negative printer, a cathode ray ( It is also suitable for a scanning exposure method using CRT). A cathode ray tube exposure apparatus is more convenient and compact than an apparatus using a laser, and is low in cost. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

The photosensitive material processed by the development processing apparatus of the present invention is a gas laser, light emitting diode, semiconductor laser, semiconductor laser, or a second harmonic generation light source combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. It is preferably exposed by a digital scanning exposure method using monochromatic high-density light such as (SHG). In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

  Preferred scanning exposure systems that can be used in combination with the apparatus of the present invention are described in detail in the patents listed in the table above. For processing the light-sensitive material of the present invention, page 26, lower right column, line 1 to page 34, upper right column, line 9 of JP-A-2-207250, and page 5, JP-A-4-97355. The processing materials and processing methods described in the upper left column, line 17 to page 18, lower right column, line 20 are preferably applicable.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, these do not limit the scope of the present invention at all.
-Light-sensitive material used in the test (preparation of blue-sensitive layer emulsion BH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. From the 80% to 90% addition of silver nitrate, potassium bromide (1.5 mol% per mole of finished silver halide) and K ₄ [Fe (CN) ₆ ] were added. K ₂ [IrCl ₆ ] was added from 83% to 88% addition of silver nitrate. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from 92% to 98% addition of silver nitrate. When 94% of the addition of silver nitrate was completed, potassium iodide (0.27 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.54 μm and a coefficient of variation of 8.5%. This emulsion was subjected to precipitation desalting treatment, and gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added thereto and redispersed.

  The redispersed emulsion was dissolved at 40 ° C., and sensitizing dye S-1, sensitizing dye S-2, and sensitizing dye S-3 of the present invention were added so as to optimize spectral sensitization. Next, sodium benzenethiosulfate, triethylthiourea as a sulfur sensitizer, and compound-1 as a gold sensitizer were added and ripened so as to optimize chemical sensitization. Thereafter, a compound in which the repeating unit 2 or 3 represented by 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-3 is a main component (terminal X1 and X2 are hydroxyl groups), compound- 4 and potassium bromide were added to terminate the chemical sensitization. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of blue-sensitive layer emulsion BL-1)
In preparation of emulsion BH-1, the temperature and the addition speed of the step of adding and mixing silver nitrate and sodium chloride at the same time were changed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.44 μm and a coefficient of variation of 9.5%. After redispersing this emulsion, Emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of BH-1.

(Preparation of green sensitive layer emulsion GH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 80% to 90% addition of silver nitrate. Potassium bromide (2 mol% per mole of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 83% to 88% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.1 mol% per mol of the finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.42 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C. and sodium benzenethiosulfate, p-glutaramide phenyl disulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (bis (1,4,5-trimethyl-1) as a gold sensitizer. , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) and ripened to optimize chemical sensitization. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. Furthermore, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion GH-1.

(Preparation of green-sensitive layer emulsion GL-1)
In preparation of Emulsion GH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amount of various metal complexes added during the addition of silver nitrate and sodium chloride is changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.35 μm and a coefficient of variation of 9.8%. After redispersing this emulsion, Emulsion GL-1 was similarly prepared except that the amount of various compounds added was changed from that of Emulsion GH-1.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. K ₄ [Ru (CN) ₆ ] was added from the time point when the addition of silver nitrate was 80% to 90%. Potassium bromide (1.3 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. K ₂ [IrCl ₅ (5-methylthiazole)] was added from 83% to 88% when silver nitrate was added. When the addition of silver nitrate was completed 88%, potassium iodide (amount of silver iodide to be 0.05 mol% per mol of finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride emulsion grains having a cube side length of 0.39 μm and a coefficient of variation of 10%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion is dissolved at 40 ° C., and sensitizing dye S-8, compound-5, triethylthiourea as sulfur sensitizer and compound-1 as gold sensitizer are added to optimize chemical sensitization. Aged. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4, and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RH-1.

(Preparation of emulsion RL-1 for red-sensitive layer)
In preparation of emulsion RH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride are changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.29 μm and a coefficient of variation of 9.9%. Emulsion RL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of Emulsion RH-1 after precipitation desalting treatment and maximum dispersion.

Preparation of first layer coating solution 34 g of yellow coupler (ExY-1), 1 g of color image stabilizer (Cpd-1), 1 g of color image stabilizer (Cpd-2), 8 g of color image stabilizer (Cpd-8), color image 1 g of stabilizer (Cpd-18), 2 g of color image stabilizer (Cpd-19), 15 g of color image stabilizer (Cpd-20), 1 g of color image stabilizer (Cpd-21), color image stabilizer (Cpd-23) 15 g, 0.1 g additive (ExC-1), 1 g color image stabilizer (UV-2) 23 g solvent (Solv-4), 4 g solvent (Solv-6), 23 g solvent (Solv-9) and acetic acid Dissolve in 60 ml of ethyl, and emulsify and disperse this liquid in 270 g of a 20% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate using a high-speed stirring emulsifier (dissolver), and add 900 g of emulsion dispersion A by adding water. did.
On the other hand, the emulsified dispersion A and the emulsions BH-1 and BL-1 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. Further, each layer Ab-1, Ab-2, and Ab-3 the total amount each ^{15.0mg / m 2, 60.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / ^{m 2} and so as Added to.

1- (3-Methylureidophenyl) -5-mercaptotetrazole was added to the second, fourth and sixth layers, 0.2 mg / m ² , 0.2 mg / m ² and 0.6 mg / m ^{2 respectively.} It added so that it might become. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is respectively 1 × 10 ⁻⁴ mol, 2 ×, per mol of silver halide. ^10-4 mol was added. 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer. The second layer, was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. Sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support: Polyethylene resin laminated paper [White pigment (TiO ₂ ; content: 16% by weight, ZnO; content: 4% by weight), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by weight) and bluish dye (ultraviolet, content 0.33% by weight) .The amount of polyethylene resin is 29.2 g / m ² )
First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.16
Gelatin 1.32
Yellow coupler (EX-Y) 0.34
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.08
Color image stabilizer (Cpd-18) 0.01
Color image stabilizer (Cpd-19) 0.02
Color image stabilizer (Cpd-20) 0.15
Color image stabilizer (Cpd-21) 0.01
Color image stabilizer (Cpd-23) 0.15
Additive (ExC-1) 0.001
Color image stabilizer (UV-A) 0.01
Solvent (Solv-4) 0.23
Solvent (Solv-6) 0.04
Solvent (Solv-9) 0.23

Second layer (color mixing prevention layer)
Gelatin 0.78
Color mixing inhibitor (Cpd-4) 0.05
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (UV-A) 0.06
Color image stabilizer (Cpd-7) 0.006
Preservative (Cpd-24) 0.006
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-8) 0.07

Third layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.12
Gelatin 0.95
Magenta coupler (ExM) 0.12
UV absorber (UV-A) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-20) 0.01
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.65
Color mixing inhibitor (Cpd-4) 0.04
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (UV-A) 0.05
Color image stabilizer (Cpd-7) 0.005
Preservative (Cpd-24) 0.005
Solvent (Solv-1) 0.05
Solvent (Solv-2) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-8) 0.06

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.10
Gelatin 1.11
Cyan coupler (ExC-1) 0.11
Cyan coupler (ExC-2) 0.01
Cyan coupler (ExC-3) 0.04
Color image stabilizer (Cpd-1) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.18
Color image stabilizer (Cpd-16) 0.002
Color image stabilizer (Cpd-17) 0.001
Color image stabilizer (Cpd-18) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-5) 0.10
Solvent (Solv-5) 0.19

Sixth layer (UV absorbing layer)
Gelatin 0.34
Ultraviolet absorber (UV-B) 0.24
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.11
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.11

Seventh layer (protective layer)
Gelatin 0.82
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.02

  The sample prepared as described above was designated as Sample 001.

2. Development processing test The sample 001 was processed into a 127 mm width roll, and a standard photographic image was exposed using a digital minilab frontier 340 (manufactured by Fuji Photo Film Co., Ltd.). Thereafter, continuous processing (running test) was performed in the following processing steps until the volume of the color developer replenisher became twice the volume of the color developer tank. However, Frontier 340 (manufactured by Fuji Photo Film Co., Ltd.) was modified so that the transport speed of the processor would be the following processing time and the tank structure was as shown in FIG.

Processing temperature Temperature Time Replenishment amount
Color development 45.0 ℃ 12 seconds 30mL
Bleach 45.0 ℃ 6 seconds 10mL
Fixing 40.0 ° C 3 seconds 10mL
Rinse 1 45.0 ° C. 3 seconds −
Rinse 2 45.0 ° C. 3 seconds −
Rinse 3 45.0 ° C. 1.5 seconds −
Rinse 4 45.0 ° C. 1.5 seconds −
Rinse 5 45.0 ° C. 1.5 seconds −
Rinse 6 45.0 ° C 1.5 seconds 80 mL
Dry 80 ° C
Note * Replenishment rate ** rinsing per photosensitive material 1 m ² was a four-tank counter-current system to (6) from (1).

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-1) 4.0 g 9.0 g
Residual color reducing agent (SR-1) 3.0 g 8.0 g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 10.0 g ―
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline
3/2 Sulfate / Monohydrate 7.0g 17.5g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with 25 ° C, sulfuric acid and KOH) 10.25 13.0

[Bleaching solution] [Tank solution] [Replenisher solution]
Water 800mL 600mL
Citric acid 19.2g 67.2g
Sulfosuccinic acid 19.4g 67.9g
Ethylenediaminetetraacetic acid iron (III)
Ammonium 47.0g 164.5g
Ethylenediaminetetraacetic acid 1.4 g 4.9 g
Nitric acid (67%) 17.5g 61.3g
m-carboxysulfinic acid 9.3 g 32.6 g
Ammonium bromide 50.0g 150.0g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 5.00 2.00

[Fixing solution] [Tank solution] [Replenisher solution]
Water 800mL 600mL
Ammonium thiosulfate (70%) 0.3 mol 1.05 mol
Ethylenediaminetetraacetic acid 1.4 g 4.9 g
Ammonium sulfite 40.0g 140.0g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.00 6.50

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5 μs / cm or less) 1000 mL 1000 mL
pH (25 ° C.) 6.5 6.5

  For comparison, continuous processing (running) was performed under exactly the same conditions except that the boundary between the bleaching tank and the fixing tank in FIG. Here, a tank having one bleaching tank and one fixing tank was a conventional bleach-fixing liquid tank, and a 1: 1 mixed solution of the above-mentioned bleaching liquid and fixing liquid was used as a starting liquid. Further, the replenishment to the bleach-fixing tank was replenished individually with the above-mentioned bleach replenisher and fixing replenisher.

  At the end of the continuous treatment, the amount of residual silver in the black high density portion and the yellow density in the white portion (minimum density portion) of the color vapor after the treatment were measured, and the results are shown in Table 1. Further, the preservative concentration (ammonium sulfite) of the rinse 1 solution was measured, and the results are shown in Table 1.

  In the processor having a bleach-fixing tank as a comparative example, the amount of residual silver in the high density black portion of the processed color paper is high in the above rapid processing, and desilvering failure occurs. Further, it is understood that the preservative concentration of the liquid in the tank of the rinse 1 is consumed until almost disappeared, and the yellow stain of the white portion of the color paper after the treatment increases corresponding to the deterioration of the rinse liquid. .

In the processor of FIG. 1 of the present invention, in the above rapid processing, there is almost no residual silver amount in the black high density part and desilvering is completed, the yellow density in the white part is low, and the preservative concentration of the rinse 1 liquid is also low. It can be seen that there is no problem with the stability of the rinse solution.
In this way, it is understood that, in continuous processing using the same processing liquid, by using the processor having the processing steps and structure of the present invention, rapid processing with good performance can be realized despite extremely rapid processing. .

It is a block diagram which shows the structure of the image development processing apparatus of the typical one aspect | mode of this invention. It is a block diagram which shows the structure of the image development processing apparatus of another typical aspect of this invention. It is sectional drawing which shows the one aspect | mode of the single blade for the passages in the liquid of the photosensitive material which concerns on this invention. It is sectional drawing which shows another aspect of the single braid | blade for the submerged passages of the photosensitive material which concerns on this invention. It is sectional drawing which shows the one aspect | mode of the double blade for the submerged passages of the photosensitive material which concerns on this invention. It is sectional drawing which shows another aspect of the double blade for submerged passages of the photosensitive material which concerns on this invention. It is sectional drawing which shows another aspect of the double braid | blade for the submerged passages of the photosensitive material which concerns on this invention.

Explanation of symbols

CD Color Developer Bleach Bleach Fix Fixer Ps-1 to Ps-6 First to sixth rinses CDO. F. Color development overflow BleachO. F. Bleach overflow FixO. F. Fixing overflow PS-1O. F. Rinse overflow 1 Color development tank 2 Bleaching tank 3 Fixing tank 4a First rinse tank 4b Second rinse tank 4c Third rinse tank 4d Fourth rinse tank 4e Fifth rinse tank 4f Sixth rinse tank 5 8a to 8b Submerged conveying path 10, 11, 12 Single blade 13, 14, 15, 16 Double blade 21a, 21b Color developing tank 22 Bleaching tank 23 Fixing tank 24a First rinse tank 24b Second rinse tank 24c Third rinse tank 24d 4th rinse tank 24e 5th rinse tank 24f 6th rinse tank 25a, 25b, 26, 27, 28a-28e Submerged conveyance path 29a-29i Single blade 30 Sealing means 31 Blade 32, 34, 35 Tank wall 32a Slit end Round part 33 Slit 36, 37 Small hole

Claims (5)

  In a development processing apparatus for silver halide color paper, each processing tank is processed with a bleaching solution following the color developer processing, and subsequently processed with a solution having a fixing ability. A halogen having a photosensitive material passage sealed in a liquid-tight manner so that a photosensitive material can pass therethrough between processing baths of a solution having a fixing ability, and the photosensitive material is conveyed in the liquid through the passage between the processing baths Development processing equipment for silver halide color paper.   2. The developing apparatus for silver halide color paper according to claim 1, wherein the processing tank for the bleaching solution and the processing tank for the liquid having fixing ability are arranged in a vertical relationship.   3. The silver halide color paper developing processing apparatus according to claim 1, wherein the total processing time of the bleaching solution and the fixing solution is 12 seconds or less.   4. The development processing apparatus for silver halide color paper according to claim 3, wherein the total processing time of the bleaching solution and the fixing solution is 10 seconds or less.   Processing tanks for all immersion processes from color developer processing to rinsing (or rinsing) processing are tanks having photosensitive material passages that are hermetically sealed so that photosensitive materials can pass between adjacent processing tanks. The silver halide color paper development processing apparatus according to claim 1, wherein the photosensitive material is conveyed in the liquid between the processing tanks.

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