JPH0566540A - Processing method for photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the processing method for a photographic sensitive material which can make ultra-rapid processing while preventing staining and obviates the contamination of photosensitive material transporting rollers. CONSTITUTION:A bleach-fixing bath contains at least one compds. among a nitrogenous heterocyclic compd. having a sulfide group, a mesoion group and thioether compd. as a fixer. The photosensitive material 20 after bleach-fixing is immersed and transported in plural washing tanks 16a to 16e, the passages of which are opened and closed by shutter means, without emerging into the air.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material excellent in desilvering property, liquid stability and less in image stain. It is about the method.

[0002]

2. Description of the Related Art Generally, the processing of a silver halide color photographic light-sensitive material comprises a color developing process and a silver removing process. In the silver removal process, the developed silver generated in the color development process is oxidized (bleached) to a silver salt by a bleaching agent having an oxidizing action, and further removed from the photosensitive layer by a fixing agent that forms soluble silver together with unused silver halide. Be done (fixed). Ferric (III) ion complex salts (for example, aminopolycarboxylic acid-iron (III) complex salts) are mainly used as bleaching agents, and thiosulfates are usually used as fixing agents. When bleaching and fixing are performed as independent bleaching and fixing steps,
In some cases, the bleach-fixing process is performed simultaneously. For details on these processing steps, see The Theory
Of Photographic Process, 4th Edition (James, "
The Theory of Photographic Process "4'th edition)
(1977). The above processing steps are generally performed by an automatic processor. In recent years, in particular, a small automatic developing machine called a minilab has been installed in stores, and a rapid processing service has been spreading to customers.
The bleaching agent and the fixing agent are used in the same bath as a bleach-fixing bath in the processing of color paper because of the downsizing of the developing machine and the rapid processing. In recent years, in particular, there has been a strong demand for speeding up of the processing step and ease of maintenance, and also for the bleach-fixing step, a drastic speeding up and improvement of liquid stability are desired. Further, since the treatment is performed in various places, the problem of treatment waste liquid has become serious.

Conventionally, ferric ethylenediaminetetraacetic acid complex salts have been used in the bleaching process. In addition, red blood salt, iron chloride, etc. are known as bleaching agents that have strong oxidizing power and achieve quick bleaching. It cannot be widely used due to inconvenience in handling such as corrosion. Recently, a ferric complex of 1,3-diaminopropanetetraacetic acid has been proposed as a versatile bleaching agent having a rapid bleaching property. However, this bleaching agent is not sufficient as a bleaching agent because bleaching fog is likely to occur during bleaching. On the other hand, thiosulfate used as a fixing agent is
In most cases, sulfite is added as a preservative to prevent oxidation because it undergoes oxidative deterioration and sulfides to form a precipitate. However, as low replenishment progresses further, improvement of liquid stability is further desired. However, with the addition of an increased amount of sulfite, solubility problems and precipitation of Glauber's salt are generated when sulfite is oxidized. , I can't solve it. Moreover, these problems become more serious as the pH of the liquid is lowered.
Also, from the viewpoint of speeding up, a compound having a better fixing property than thiosulfate is desired.

Further, when the rapid bleach-fixing treatment is carried out after the rapid color development, the sensitizing dye used in the developing agent or the light-sensitive material, which has been conventionally removed in the bleach-fixing step, does not sufficiently remove the dye and the like, Therefore, stains have begun to appear on the processed image. Therefore, development of a fixing agent and a bleaching agent that solve the above problems, and a processing composition and a processing method using them have been strongly desired. In view of such problems, the present inventors have conducted various studies on fixing agents which are superior in oxidative stability instead of thiosulfates, and as a result, at least one of a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound or a thioether compound has been obtained. By using a bleach-fixing solution containing a compound, it is stable against oxidation and does not produce a precipitate even at a low replenishing amount, and the bleaching fog is smaller than that of thiosulfate salt, and in particular, it is combined with a high potential oxidizing agent. It has been found that good results are obtained with bleach-fix.

[0005]

However, in the short processing time of bleach-fixing, the color developing agents, sensitizing dyes, dyes and the like brought in from the color developing bath are not sufficiently removed as described above, and all the processing steps are carried out. It has become difficult to shorten the bleach-fixing processing time as the length of the sheet becomes shorter. In particular, the removal of the developing agent is a serious problem, and when the bleach-fixing time and the washing or stabilizing treatment time are shortened, stains are noticeably formed on the image, and the adverse effect thereof is observed. It was also found that the lower the pH of the bleach-fixing bath, the better the removal of the developing agent, and that it was good at a pH of 5 or less.

Further, when processing is performed using the above fixing agent,
It was found that the fixing agent and the silver salt adhered to the photosensitive material conveying roller during the dispersal processing. Here, the quiet processing refers to the following cases. When the processing amount per day is small or the processing time is short. When the amount of processing that is running per unit time is low. When the interval between operations is long. For example, when the processing time for one operation is short (the processing amount is small) and the stop time is relatively long, or when the operation time is long but the stop time until the next processing is long. If a fixing agent or a silver salt adheres to and stains the transport roller during such a dusting process, these are transferred to the photosensitive material and stain the photosensitive material. Therefore, it is necessary to clean the transport roller frequently.

An object of the present invention is to solve the above problems, and to provide a method for processing a photographic light-sensitive material, which is capable of preventing stains and performing ultra-rapid processing, and in which a roller for conveying the photographic light-sensitive material is not stained. To provide.

[0008]

The above object of the present invention is achieved by the processing methods described in (1) to (4) below. (1) In a method of exposing and then developing a photographic light-sensitive material having at least one layer of a photosensitive silver halide emulsion on a support, a nitrogen-containing heterocyclic compound having a sulfide group as a fixing agent after development, A photograph characterized by being treated with a bath having a fixing ability containing at least one compound of a mesoionic compound or a thioether compound, and then being washed and / or stabilized by a multi-stage countercurrent bath without exposing the light-sensitive material to air. Method of processing photosensitive material. (2) The silver halide emulsion contains 90 mol% of silver chloride.
2. The method for processing a photographic light-sensitive material according to claim 1, which contains the above particles. (3) The photosensitive material is brought into contact with the peripheral surface of the processing roller provided in the processing liquid of the multi-stage countercurrent bath so that the absolute value of the peripheral speed of the processing roller becomes larger than the absolute value of the photosensitive material conveying speed. 3. The method for processing a photographic light-sensitive material according to claim 1, wherein the processing roller is rotated at 75 rpm or more for processing. (4) The method for processing a photographic light-sensitive material according to any one of claims 1 to 3, wherein the bath for washing and / or stabilizing treatment has an opening ratio of 0.001 or less.

When the washing and / or stabilizing treatment is carried out in a multi-stage countercurrent bath, the photosensitive material is moved in water between the tanks so as not to come into contact with air. A photosensitive material passage is formed between the layers so that the photosensitive material can move in water, and the passage is opened and closed by shutter means. The shutter means can be constructed by providing a pair of flexible blades so that only their tips are elastically in contact with each other. By moving the light-sensitive material in the water between the washing baths in this way, the generation of stains can be suppressed. By using a light-sensitive material using a high silver chloride emulsion having no or little silver iodide and silver bromide, it is possible to prevent deposits and stains from increasing on the conveying roller. Stable even when subjected to a quiet treatment and / or a low replenishment treatment by treating with a bath having a fixing ability containing at least one compound of a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound or a thioether compound as a fixing agent. It has good properties and does not cause precipitation or turbidity. Further, the image stain is small even when washed with water for a short time, and the stain over time after the image is stored for a long time is also small. At least one compound selected from the nitrogen-containing heterocyclic compound, the mesoionic compound and the thioether compound is preferably contained in an amount of 0.1 mol / liter or more. The processing solution in the present invention does not need to contain sulfite, so that it becomes possible to squeeze or strongly stir with a blade or the like in the water washing process, and to wash out unnecessary components (developing agent, dye, etc.) from the light-sensitive material in a short time. It will be possible.

The processing time according to the present invention is preferably within 25 seconds in the bleach-fixing process and within 120 seconds from the beginning of the developing process to the end of the drying process. In bleach-fixing for a short period of time, a large amount of developing agent is accumulated in the light-sensitive material to generate stain, and it is difficult to sufficiently remove silver salt. In particular, p-phenylenediamine type color developing agents have a large tendency. However, the unnecessary substance is easily removed by passing the photosensitive material between the plates in water. Further, the processing time is further shortened by providing a rotating processing roller in the liquid and processing the photosensitive material in contact with the peripheral surface of the processing roller. The rotation speed of the processing roller is 75 rp
It is preferably m or more, and the rotation direction may be the same as or opposite to the photosensitive material conveyance direction. In the processing of the present invention, the bleach-fixing solution contains at least one metal chelate compound consisting of compounds represented by the following general formulas (I), (II), (III), (IV) and (V). Preferably. General formula (I)

[0011]

[Chemical 1]

In the formula, X is --CO--N (OH)-R _a ,-
N (OH) -CO-R _b (where R _a represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. R _b represents an aliphatic group, an aromatic group, or a heterocyclic group. ), -SO ₂
NR _c (R _d ) or —N (R _e ) SO ₂ R _f (wherein R _c , R _d and R _e represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R _f is a fat Represents a group group, an aromatic group or a heterocyclic group). L ₁ represents a divalent linking group containing a group consisting of an aliphatic group, an aromatic group, a heterocyclic group or a combination thereof. R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. General formula (II)

[0013]

[Chemical 2]

In the formula, R ₂₁ has the same meaning as R _{11 in} formula (I). R _2a and R _2b may be the same or different and each is —Y ₁ —C (═X ₁ ) —N (R _h ) —R _g or —Y ₂
-N (R _i ) -C (= X ₂ ) -R _j (wherein Y ₁ and Y ₂ have the same meanings as L _{1 in} formula (I). R _g , R _h, and R _i are represented by formula (I I) has the same meaning as R _a , R _j is an aliphatic group, an aromatic group, a heterocyclic group, —NR _k (R _l ) (where R _k and R _l are the same as R _a of the general formula (I)). Have the same meaning) or -OR _m (wherein R _m represents an aliphatic group, an aromatic group or a heterocyclic group), and X ₁ and X ₂ represent an oxygen atom or a sulfur atom. . General formula (III)

[0015]

[Chemical 3]

In the formula, R ₃₁ , R ₃₂ and R ₃₃ are represented by the general formula (I)
Is synonymous with R ₁₁ of. R _3a has the same _meaning as R _{2a in} formula (II). W represents a divalent linking group. General formula (IV)

[0017]

[Chemical 4]

In the formula, R ₄₁ and R ₄₂ are R _{11 of the} general formula (I).
Is synonymous with. L ₂ represents a divalent linking group. Z represents a heterocyclic group. n represents 0 or 1. General formula (V)

[0019]

[Chemical 5]

In the formula, L ₃ represents a divalent linking group containing an aliphatic group, an aromatic group, a heterocyclic group or a combination thereof. A represents a carboxy group, a phosphono group, a sulfo group or a hydroxy group. R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R
₅₅ , R ₅₆ and R _{57, which} may be the same or different, each represents a hydrogen atom, an aliphatic group or a heterocyclic group. R ₅₈ and R
₅₉ may be the same or different and each is a hydrogen atom, an aliphatic group,
Aromatic group, heterocyclic group, halogen atom, cyano group, nitro group, acyl group, sulfamoyl group, carbamoyl group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfinyl group. Also R
₅₈ and R ₅₉ may combine to form a ring. t and u represent 0 or 1.

The present invention enables rapid water washing and / or stabilization treatment, and also enables treatment to be carried in the treatment bath, which can be treated without substantially contacting air, and can be opened. It is possible to perform a sufficiently satisfactory process even with a processing device having a small rate. Further, a low replenishment amount can be processed for the same reason. The opening ratio in the present invention is a value obtained by dividing the surface area of the processing tank by the volume of the processing tank, and is often used as an index of the oxidizability of the processing liquid in the processing tank. In the present invention, the temperature of the washing and / or stabilizing bath is 3
It was also found that the temperature is preferably 0 ° C. or higher, and particularly when the temperature is 40 ° C. or higher, the above-mentioned substance that imparts stain to the image can be rapidly removed. However, when the temperature is 40 ° C. or higher, the evaporation of water becomes extremely large, and it is preferable that the aperture ratio is 0.001 or less.

The present invention is a processing method intended for rapid and simple processing, and a light-sensitive material having an alkali consumption of 3.0 mmol / m ² or less can be preferably used. Alkali consumption means, as described in JP-A-3-109549, a photosensitive material is pulverized using a support to adjust the pH from 6 to 1.
Define the required amount of alkali needed to raise to zero. As the bleach-fixing composition in the present invention, a bleach-fixing solution is generally used, but it also means a replenishing solution, a supply kit (solution or a sticky agent) and the like. The replenisher may be divided into two or more types and replenished. General formula (I), (II), (III), (IV)
Specific examples of compounds represented by and / or (V) and synthetic methods are disclosed in Japanese Patent Application Nos. 2-127,479 and 2-175.
026, 2-196,972, 2-201,8
46, 2-258,539. Representative examples of the compounds represented by formulas (I), (II), (III), (IV) and / or (V) are shown below, but the invention is not limited thereto.

[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

The central metal used in the metal chelate compound is, for example, Fe (III), Mn (III), Co (III),
Rh (II), Rh (III), Au (III), Au (II), Ce (I
V) and the like. The metal chelate compound may be isolated as a metal chelate compound. Of course, in the present invention, the general formula (I), (II), (III), (IV)
And / or a compound represented by (V) and a metal salt, for example, ferric sulfate complex salt, ferric chloride salt, ferric nitrate salt, ferric ammonium sulfate, ferric phosphate salt, etc. You may use it by making it react inside. General formula (I), (II), (II
The compounds represented by I), (IV) and / or (V) are used in a molar ratio of 1.0 or more with respect to the metal ion. This ratio is preferably larger when the stability of the metal chelate compound is low, and is usually used in the range of 1 to 30. Specific examples of the nitrogen-containing heterocyclic compound having a sulfide group of the present invention are shown below, but the present invention is not limited thereto.

[0028]

[Chemical 10]

The nitrogen-containing heterocyclic compound having a sulfide group used in the present invention is Berichte der Deu
tschen Chemischen Gesellschaft) 28, 77 (189)
5), JP-A Nos. 50-37436 and 51-3231.
U.S. Pat. No. 3,295,976, U.S. Pat. No. 3,37
6,310, Berichte der Deutschen Che
mischen Gesellschaft) 22, 568 (1889), 29, 2483 (1896), Journal of Chemical Society (J. Chem. Soc.) 1932, 180.
6. Journal of the American Chemical Society (J. Am. Chem. Soc.) 71, 4000 (194)
9), US Pat. Nos. 2,585,388 and 2,541,
924, Advances in Heterocyclic Chemistr
y) 9, 165 (1968), Organic Syntheses IV, 569 (1963), Journal of the American Chemical Society (J. Am. Chem. Soc.) 45, 2390 (192).
3), Chemische Berichte
9, 465 (1876), Japanese Patent Publication No. 40-28496,
JP-A-50-89034, U.S. Pat. No. 3,106,46
No. 7, No. 3,420,670, No. 2,271,229
Issue 3, 137,578, Issue 3,148,066
No. 3,511,663, No. 3,060,028
Issue 3, Issue 271,154, Issue 3,251,691
Issue No. 3,598,599 Issue 3,148,066
Japanese Patent Publication No. 43-4135, U.S. Pat. No. 3,615,6
No. 16, 3,420,664, 3,071,46
No. 5, No. 2,444,605, No. 2,444,606
No. 2,444,607, No. 2,935,404 and the like. Specific examples of the mesoionic compound of the present invention are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 11]

[0031]

[Chemical formula 12]

The mesoionic compound of the present invention is prepared according to the Journal of Heterocyclic Chemistry (J. Het.
erocyclic Chem.) 2, 105 (1965), Journal of Organic Chemistry (J. Org. Chem.)
32, 2245 (1967), Journal of Chemical Society (J. Chem. Soc.) 3799 (196).
9), Journal of American Chemical Society (J. Am. Chem. Soc.), 80, 1895 (195).
8), Chemical Communication (Chem.Commun.)
1222 (1971), Tetrahedron Letters (Te
trahedron Lett.) 2939 (1972), JP-A-60-
87322, Berichte der Deutschen Che
mischenGesellschaft) 38, 4049 (1905),
Journal of Chemical Society Chemical Communication (J. Chem.Soc.Chem.Commun.) 1
224 (1971), JP-A-60-122936, JP-A-60-117240, Advances in Heterocyclic Chemistry (Advances in Hetero).
Cyclic Chemistry 19, 1 (1976), Tetrahedron Letters 5881 (19)
68), Journal of Heterocyclic Chem. (J. Heterocyclic Chem.) 5, 277 (196).
8), Journal of Chemical Society Perkin Transaction I (J. Chem. Soc., Perkin Tr
ans. I) 627 (1974), Tetrahedron Letters 1809 (1967), ibid. 1
578 (1971), Journal of Chemical Society (J. Chem. Soc.) 899 (1935), 2
865 (1959), Journal of Organic Chemistry (J. Org. Chem.) 30, 567 (196).
It can be synthesized by the method described in 5) or the like. Specific examples of the thioether compound of the present invention are shown below, but the present invention is not limited thereto.

[0033]

[Chemical 13]

[0034]

[Chemical 14]

The above-mentioned thioether compound of the present invention is used in the Journal of Organic Chemistry (J. Org.
m.) 30, 2867 (1965), ibid. 27, 2846
(1962), Journal of American Chemical Society (J. Am. Chem. Soc.) 69, 2330.
It can be easily synthesized by referring to (1947) and the like.

The color photographic paper in the color photographic light-sensitive material used in the present invention has at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on the support. It can be constructed by coating. In general color photographic printing paper, it is usual that the color printing paper is coated on the support in the order described above, but the order may be different from this. The imaging system containing the light-sensitive materials and processes which can be used in the present invention can be used for the rapid processing of commonly used color prints, but can also be used for intelligent color hard copy applications where increased speed is more desirable. In particular, as an aspect of the intelligent color hard copy, an aspect in which scanning exposure is performed by using a high density light such as a laser (for example, a semiconductor laser) or a light emitting diode is preferable. Many semiconductor lasers have high photosensitivity in the infrared region, and the light-sensitive material used for that purpose can use an infrared-sensitive silver halide emulsion layer in place of at least one of the above emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having sensitivity in each wavelength region and a dye having a complementary color relationship with the light to be exposed, that is, yellow for blue, magenta for green and cyan for red are formed. By incorporating such a so-called color coupler, color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the coloring hue of the coupler may not have the above correspondence.

Further, the color coupler may have two colors depending on the required image quality and quality. In this case, the number of silver halide emulsion layers corresponding to each may be two. In this case, a full-color image is not obtained, but the image can be formed more quickly. As the silver halide emulsion used in the present invention, silver chlorobromide or silver chloride containing 90 mol% or more of silver chloride is used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any portion of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition or a structure having a portion having a different halogen composition inside or on the surface of the particle (edge of the particle when present on the particle surface, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two particles rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

On the other hand, in the high silver chloride emulsion used in the present invention having a silver chloride content of 90 mol% or more, the distribution of the halogen composition in the grains is controlled in order to suppress the sensitivity deterioration when the light-sensitive material is subjected to pressure. It is also preferable to use particles having a small uniform structure. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used. The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is determined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is preferably 0.1 μm to 2 μm. .. The particle size distribution of these particles is the coefficient of variation (standard deviation of the particle size distribution divided by the average particle size).
% Or less, preferably 15% or less, so-called monodisperse particles are preferable. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate. ) Those having a crystalline form or those having a composite form thereof can be used. It may also be a mixture of those having various crystal forms. In the present invention, among these, particles having the above-mentioned regular crystal form are
It is preferable to contain 50% or more, preferably 70% or more, more preferably 90% or more.

In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains is also preferably used. it can. The light-sensitive material according to the present invention comprises a hydrophilic colloid layer for the purpose of improving the sharpness of an image, a dye decolorizable by treatment described in European Patent EP 0,337,490A2, pages 27 to 76. Among them, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or a dihydric or tetrahydric alcohol (for example, trimethylolethane) is added to the water resistant resin layer of the support. It is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with (1) or the like. Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds to the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the aroma remaining after the color development processing. The simultaneous use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, for example, in storage after processing. It is preferable in order to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the residual color developing agent in the film or its oxidation product.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has the anti-photosensitive property described in JP-A-63-271247. It is preferable to add a fungicide. The support used in the light-sensitive material according to the present invention may be a white polyester-based support for a display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. In addition, in exposing, U.S. Pat.
It is preferred to use the band stop filter described in 880,726. As a result, the light color mixture is removed, and the color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to color development processing, but for the purpose of rapid processing, it is preferable to perform bleach-fix processing after color development. Especially when the above high silver chloride emulsion is used, the pH of the bleach-fix solution is
Is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing the light-sensitive material. As additives, the following patent publications, particularly European Patent EP0,355,660A2 (Japanese Patent Application No.
1-107011) The following Table A described in the specification is preferably used.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

Further, as a cyan coupler, JP-A-2-33
In addition to the diphenylimidazole-based cyan couplers described in JP-A-144, 3-hydroxypyridine-based cyan couplers (especially the couplers (42) listed as specific examples) described in EP 0,333,185A2. A 4-equivalent coupler having a chlorine-releasing group to make it a 2-equivalent compound, couplers (6) and (9) are particularly preferable), and cyclic active methylene cyan couplers described in JP-A-64-32260 (Naka) However, coupler examples 3 and 8 listed as specific examples,
(3 and 4 are particularly preferable) are also preferable. The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing and washing treatment (or stabilization treatment). Bleaching and fixing may be performed separately instead of the one bath as described above.

Known color developing agents are used in the invention, and representative examples thereof are shown below, but the invention is not limited thereto. D-1 4-Amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline D-2 4-Amino-N-ethyl-N- (3-hydroxypropyl) -3-methylaniline D- 3 4-Amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline D-4 4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline D- 5 4-amino-N- (3-carbamoylpropyl-Nn-propyl-3-methylaniline

Of these, particularly preferred is exemplary compound D
-3 and D-4. Such a main drug is effective in the replenishment method of the present invention. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid, etc. may be used. The amount of the aromatic primary amine developing agent used is preferably 1 liter of the developing solution (as a tank solution).
The amount is 0.002 mol to 0.2 mol, and more preferably 0.005 mol to 0.1 mol. In the practice of the present invention, it is preferable to use a developing solution containing substantially no benzyl alcohol. Here, the term "substantially free from" means that the concentration of benzyl alcohol is preferably 2 ml / l or less, more preferably 0.5 ml / l or less, and most preferably benzyl alcohol is not contained at all. It is more preferable that the developer or its replenisher used in the present invention contains substantially no sulfite ion. Sulfite ion is
At the same time as a function as a preservative for the developing agent, it has a function of dissolving a silver halide and a function of reacting with an oxidized product of the developing agent to reduce the dye forming efficiency. It is presumed that such an action is one of the causes of the increase in fluctuations in photographic characteristics associated with continuous processing. Here, the term "substantially free from" means that the concentration of the sulfite ion is preferably 0.10 mol or less with respect to 1 mol of the developing agent, and most preferably, the sulfite ion is not contained at all. However, in the present invention, a very small amount of sulfite ion used for the oxidation prevention of the processing agent kit in which the developing agent is concentrated before being adjusted to the use solution is excluded.

The developer used in the present invention preferably contains substantially no sulfite ion, and more preferably contains substantially no hydroxylamine. This is because it is considered that hydroxylamine itself has a silver developing activity at the same time as a function as a preservative of the developing solution, and fluctuations in the concentration of hydroxylamine greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means preferably 5.0 × 10 ^-3 mol /
Hydroxylamine concentrations of less than one liter, most preferably no hydroxylamine at all. The color developer and its replenisher used in the present invention are
It is more preferable to contain an organic preservative in place of the hydroxylamine or sulfite ion. Here, the organic preservative means that when added to the processing solution of the color photographic light-sensitive material,
Aromatic primary amine Refers to all organic compounds that reduce the rate of deterioration of color developing agents. That is, although it is an organic compound having a function of preventing the oxidation of the color developing agent due to air, etc., among them, a hydroxylamine derivative (excluding hydroxylamine; hereinafter the same), hydroxamic acids, hydrazines, hydrazides, phenols, Particularly, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. It is an effective organic preservative. These are disclosed in JP-A-63-4235,
63-30845, 63-21647, 63-44655, 63-53551
63, 43-140, 63-56654, 63-58346, 63
-43138, 63-146041, 63-44657, 63-44656
U.S. Pat.Nos. 3,615,503 and 2,494,903.
No. 52-143020, Japanese Examined Patent Publication No. 48-30496, etc.

Other preservatives include various metals described in JP-A-57-44148 and 57-53749, and JP-A-59-180.
Salicylic acids described in JP-A-588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, and U.S. Pat.
The aromatic polyhydroxy compound described in the specification No. 4 and the like may be contained if necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferable. Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferable, and the details thereof are described in JP-A-1-97953, 1-186939, 1-186940, Ibid 1-18
It is described in Japanese Patent No. 7557 and the like. Further, it is more preferable to use the above hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developing solution, and thus improving the stability during continuous processing.

As the above amines, JP-A-63-23944
Cyclic amines such as those described in JP-A-7 and JP-A-63-1
The amines described in JP-A-28340 and other amines such as those described in JP-A Nos. 1-186939 and 1-187557. Further, in the present invention, as the hydroxylamine derivative, those represented by the following general formula (I) are preferably used. General formula (I)

[0052]

[Chemical 15]

(In the formula, L represents an alkylene group which may be substituted, A is a carboxyl group, a sulfo group, a phosphone group, a phosphine group, a hydroxyl group, an amino group which may be alkyl-substituted or an alkyl group which may be alkyl-substituted. A good ammonio group, a carbamoyl group which may be alkyl-substituted, a sulfamoyl group which may be alkyl-substituted, an alkylsulfonyl group which may be substituted, and R represents a hydrogen atom or an alkyl group which may be substituted. Specific compounds of the hydroxylamine derivative used in the present invention are described in, but the present invention is not limited thereto.

[0054]

[Chemical 16]

Specific examples of sulfinic acid and salts thereof used in the present invention are listed below.

[0056]

[Chemical 17]

The above compounds can be used alone or as a mixture of two or more kinds. The sulfinic acid can be synthesized by, for example, the method described in JP-A-62-143048 or a method analogous thereto. The content of sulfinic acid used in the present invention is 0.001 to 1.0 mol / liter, preferably 0.002 to 0.2 mol / liter. Chlorine ions in the color developer in the present invention are 3.5 × 10 ⁻³ to 3.0 × 10.
It is preferable to contain ^-1 mol / liter. Particularly preferably, it is 1 × 10 ^-2 to 2 × 10 ^-1 mol / liter. When the chlorine ion concentration is more than 3.0 × 10 ^-1 mol / liter, it has the drawback of delaying the development, which is not preferable for achieving the object of the present invention that it is rapid and the maximum concentration is high. Further, if it is less than 3.5 × 10 ⁻³ mol / liter, it is not preferable for preventing fog.

In the present invention, it is preferable that the color developing solution contains bromine ions in an amount of 0.5 × 10 ⁻⁵ mol / liter to 1.0 × 10 ⁻³ mol / liter. More preferably 3.0
× 10 ^{-5 to} 5 × 10 ^-4 mol / liter. When the bromine ion concentration is higher than 1 × 10 ^-3 mol / liter, development is delayed, the maximum concentration and sensitivity are lowered, and when it is less than 0.5 × 10 ^-5 mol / liter, fog cannot be sufficiently prevented. .. Here, chlorine ion and bromine ion may be directly added to the developing solution, or may be eluted from the light-sensitive material to the developing solution during the development processing. When added directly to the color developing solution, examples of chlorine ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride. Are sodium chloride and potassium chloride. It may also be supplied from a fluorescent whitening agent added to the developer. As a source of bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred is potassium bromide,
It is sodium bromide.

When the light-sensitive material is eluted during the development process,
Both chlorine ion and bromine ion may be supplied from the emulsion, or may be supplied from other than the emulsion. The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution may contain compounds of other known developing solution components. Above pH
It is preferable to use various buffering agents in order to retain the. As the buffering agent, 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, etc. Can be used. Especially, carbonate, phosphate, tetraborate and hydroxybenzoate are highly soluble and have a pH of 9.0 or higher.
It is particularly preferable to use these buffers, because they have excellent buffering ability in the pH range, have no adverse effect on the photographic performance (fogging, etc.) even when added to the color developing solution, and are inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
2-hydroxybenzoic acid potassium (potassium 5-sulfosalicylate) etc. can be mentioned. However, the present invention is not limited to these compounds.
The amount of the buffer added to the color developer and its replenisher is 0.
It is preferably 1 mol / liter or more, particularly 0.1
It is particularly preferable that the amount is from mol / liter to 0.4 mol / liter. In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ',
N'-tetramethylene sulfonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid,
Glycol ether diamine tetraacetic acid, ethylenediamine ortho hydroxyphenyl acetic 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-hydroxybenzene- 4,6-disulfonic acid and the like can be mentioned.

Two or more of these chelating agents may be used in combination, if desired. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 to 10 g per liter. If necessary, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication Nos. 37-16088 and 37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9019, and U.S. Pat.No. 3,813,247, etc.
-Phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, JP-B-44-30074 and JP-A-SHO
56-156826 and 52-43429, and the like, quaternary ammonium salts, U.S. Pat. Nos. 2,494,903 and 3,128,
No. 182, No. 4,230,796, No. 3,253,919, and Japanese Patent Publication No. 41-1
1431, U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,346, etc., or amine compounds described in the specification, JP-B-37-16088, 42-25201, U.S. Pat.
3,128,183, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat. No. 3,532,501.
-Pyrazolidones, imidazoles, etc. and ascorbic acid can be added as required. In replenishment, an optional antifoggant can be added, if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrohenimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4 / liter. Also, if necessary, various known water-soluble polymers of polyvinyl alcohol, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, polyvinyl pyrrolidone, or copolymers thereof, alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid Various surfactants such as aromatic carboxylic acid polyethylene oxide may be added. The processing temperature of the color developer applicable to the present invention is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 120 seconds, preferably 10 seconds to 60 seconds. It is preferable that the replenishing amount is small, but ^{20 to} 600 ml per 1 m ^{2 of} the light-sensitive material is suitable,
It is preferably 120 ml or less. More preferably 60 ml,
It is preferable in that the effects of the present invention can be effectively exhibited. Also,
In the color development of the present invention, the liquid opening ratio (air contact area (cm
² ) / liquid volume (cm ³ )) has relatively excellent performance in any state as compared with combinations other than the present invention, but the liquid opening ratio is 0 to 0.1 from the viewpoint of stability of the color developing solution.
cm ^-1 is preferred. In continuous processing, practically 0.
The range of 001 cm ^{-1 to} 0.05 cm ^-1 is preferable, and 0.002 to 0.03 cm ^-1 is more preferable. Next, the desilvering process applicable to the present invention will be described. The desilvering step may be generally used in any step such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step.

The bleaching solution, the bleach-fixing solution and the fixing solution applicable to the present invention will be described below. As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used, but in particular, organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolycarboxylic acids Preferred are phosphonic acid, phosphonocarboxylic acid and organic phosphonic acid complex salts) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide. Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of hourly treatment and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid and glycol etherdiaminetetraacetic acid. These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-
Diaminopropane tetraacetic acid, methyliminodiacetic acid iron (II
I) Complex salts are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. In addition, the chelating agent may be used in excess of the amount required to form the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and more preferably, the metal chelate compound consisting of the compounds represented by the general formulas (I), (II), (III), (IV) and (V). It is preferable to contain at least one. The amount added is 0.01 to 1.0 mol / liter, preferably 0.05 to 0.50 mol / liter.

Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, U.S. Pat. No. 3,893,858, German Patent No. 1,290,812, Japanese Patent Laid-Open No. 53-95630, Research Disclosure No. 17129 (July 1978).
Compounds having a mercapto group or a disulfide bond described in JP-B-45-8506 and JP-A-52-20832.
No. 53-32735, US Pat. No. 3,706,561 and the like, or thiourea compounds described in the specification or halides such as iodine and bromine ions are preferable because of their excellent bleaching power. In addition, the bleaching solution or bleach-fixing solution applicable to the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide), chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. Rehalogenating agents such as halides (eg, ammonium iodide) can be included. If necessary, one or more inorganic acids having pH buffering ability, such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The bleach-fixing solution or the fixing agent used in the fixing solution is a nitrogen-containing heterocyclic compound having the above sulfide group,
It is a silver halide dissolving agent such as a mesoionic compound or a thioether compound, and these can be used alone or in combination of two or more. The amount of the fixing agent per liter is preferably 0.1 mol or more, more preferably 0.3 mol.
It is in the range of up to 2.0 mol. The pH range of the bleach-fixing solution or the fixing solution is preferably 2-8, and more preferably 3-5. Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like. The bleach-fixing solution and fixing solution include sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite. It is preferable to contain a sulfite ion-releasing compound such as (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). These compounds are preferably contained in an amount of about 0.02 to 0.05 mol / liter in terms of sulfite ion, and more preferably 0.04 to
It is 0.40 mol / liter. In addition, ascorbic acid, sulfinic acid carbonyl bisulfite adduct, or carbonyl compound may be added. Further, a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent, etc. may be added as required. The bleach-fixing solution of the present invention has a processing time of 5 seconds to 120 seconds, preferably 10 seconds to 60 seconds. The temperature is 25 to 60 ° C, preferably 30 to 50 ° C. The replenishing amount is ²⁰ ml to 250 per 1 m ² of the light-sensitive material.
ml, preferably 30 ml to 100 ml. After desilvering such as fixing or bleach-fixing, it is generally washed with water and / or stabilized (hereinafter, stabilizing is included in washing unless otherwise specified).

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler) and the application, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 5. According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, 0.5 liter to 1 liter or less per 1 m ^{2 of the} light-sensitive material is possible, and the effect of the present invention is remarkable, but the water in the tank Due to the increase of the residence time, bacteria grow and problems such as adherence of the produced floating substances to the light-sensitive material occur. As a solution to such a problem,
The method for reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-267761. It is also possible to use bactericides such as the described benzotriazole and copper ions. Furthermore,
For aqueous water, a surfactant as a draining agent and a chelating agent represented by EDTA as a water softener can be used.

It is also possible to carry out treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart antifungal property to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used. Furthermore,
Surfactants, fluorescent brighteners and hardeners can also be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without undergoing a washing step, it is disclosed in JP-A-57-8543.
All known methods described in JP-A Nos. 58-14834 and 60-220345 can be used. In the present invention, the washing and / or stabilizing water may be treated with a reverse osmosis membrane. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, and poly (vinylidene carbonate) can be used. However, since a decrease in permeated water is particularly likely to occur, a crosslinked polyamide-based composite membrane, polysulfone-based Composite membranes are preferred.
In addition, from the viewpoints of equipment initial cost reduction, running cost reduction, downsizing, noise prevention of pump, etc.,
A low pressure reverse osmosis membrane that can be used at a low delivery pressure of kg / cm ² is preferable. Furthermore, the structure of the membrane is preferably a spiral membrane in which a flat membrane is wound into a roll shape, because the amount of permeated water is less likely to decrease.

The liquid feeding pressure in the use of these membranes is in the range as described above, but preferable conditions are ^{2 to} 10 kg / cm ² , and particularly preferable conditions are 3 to 7 kg / cm ^{2 for} the stain prevention effect and the prevention of reduction of the amount of permeated water. It is cm ² . The washing and / or stabilizing process is preferably connected in a multi-stage countercurrent system with a plurality of tanks, but it is particularly preferable to use 2 to 5 tanks. The treatment with the reverse osmosis membrane is preferably performed on the water in the second tank and subsequent tanks for such multistage countercurrent washing and / or stabilization. Specifically, in the case of a two-tank configuration, the second tank, in the case of a three-tank configuration, the second or third tank, and in the case of a four-tank configuration, the water in the third or fourth tank is treated with a reverse osmosis membrane and permeated. It is carried out by returning the water to the same tank (the tank in which water is collected for the reverse osmosis membrane treatment; hereinafter referred to as a collection tank) or the washing and / or stabilizing tank located thereafter. Furthermore, it is also possible to return the concentrated washing and / or stabilizing solution to the bleach-fixing bath upstream of the sampling tank.

A chelating agent can be used in the washing bath of the present invention. The chelating agent that can be used may be selected from aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, alkylidene diphosphonic acid, metaphosphoric acid, pyrophosphoric acid, organic phosphonic acid or salts thereof and polyphosphoric acid. it can. Especially Japanese Patent Application 2-4
It is preferable to contain the organic phosphonic acid compound described in No. 0940. The amount of these organic phosphonic acids and / or organic phosphonates added to the washing or stabilizing bath can be determined by the amount of ferric ethylenediaminetetraacetate contained in the light-sensitive material. Bath 1
An addition amount of 2.9 to 290 mmol per liter is preferred. More preferably, it is 14.6 mmol to 146 mmol. If the added amount is too large, the surface may become sticky, and conversely, if the added amount is too small, the original stain improving effect is not obtained. It is also a preferable embodiment to use magnesium or a bismuth compound. In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound. A so-called rinse solution is also used as a washing solution or a stabilizing solution used after the desilvering process.

The pH of the washing step or stabilizing step is preferably 4-10, more preferably 5-8. The temperature can be set variously depending on the use and characteristics of the light-sensitive material, but in general it is 30
-60 ° C, preferably 35-50 ° C. The time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing the processing time. It is preferably 5 seconds to 45 seconds, more preferably 10 seconds to 35 seconds. The smaller the replenishment amount, the more preferable from the viewpoint of running cost, reduction of discharge amount, handleability, and the like. A specific preferable amount of replenishment is 0.5 to 50 times, preferably 2 to 15 times the carry-in amount per unit area from the pre-bath. Alternatively, it is 300 ml or less, preferably 150 ml or less, per 1 m ^{2 of the} light-sensitive material. The replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be further used in the previous step. As an example of this, it is possible to reduce the amount of waste liquid by reducing the overflow of washing water by a multi-stage countercurrent system to flow into the bleach-fixing bath of the preceding bath and replenishing the bleach-fixing bath with a concentrated solution. In the present invention,
A so-called jet jet can be carried out in the wash water and / or the stabilizing solution or any other treating solution. The jet flow can be generated by sucking the processing liquid in the processing bath with a pump and discharging the processing liquid toward the emulsion surface from a nozzle or a slit provided at a position facing the emulsion surface of the light-sensitive material. More specifically, JP-A-62-183
The method described in JP-A No. 460, page 3, lower right column to page 4, lower right column, in which the liquid pumped by a pump is discharged from a slit or nozzle provided facing the emulsion surface can be adopted. . The processing step time of the present invention is defined as the time from the contact of the light-sensitive material with the color developing solution to the final bath (generally, washing or stabilizing bath),
The effect of the present invention is remarkably exhibited in the rapid processing step in which the processing step time is 3 minutes or less, preferably 1 minute 30 seconds or less.

The drying process that can be used in the present invention will be described. A drying time of 20 to 40 seconds is desired in order to complete an image by the ultra-rapid processing of the present invention. As a means for shortening the drying time, as a means on the side of the light-sensitive material, it is possible to improve by reducing the amount of water taken into the film by reducing the amount of a hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-in amount, it is also possible to accelerate the drying by absorbing the water with a squeeze roller or a cloth immediately after leaving the washing bath. As a means of improvement from the dryer, it goes without saying that the temperature can be increased and the drying air can be increased to accelerate the drying. further,
The drying can be speeded up by adjusting the irradiation angle of the dry air to the sensitive material and the method of removing the exhaust air.

[0072]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited to this embodiment. FIG. 1 shows a silver salt photographic color paper processor to which the present invention is applied. This processor develops, bleach-fixes, and exposes web-shaped color paper exposed based on positive originals.
After washing with water and drying, an image is formed on a color paper. A color paper (hereinafter referred to as a light-sensitive material) processed by this processor is a color photographic light-sensitive material having at least one layer of a silver halide emulsion containing 95 mol% or more of silver chloride on a support, and is aromatic. Color development is performed with a color developing solution containing a primary amine color developing agent.

The processor main body 10 is provided with a developing tank 12, a bleach-fixing tank 14, washing tanks 16a to 16e, a draining section 17 and a drying section 18 in succession. The photosensitive material 20 after exposure is subjected to development and bleach-fixing. After being washed with water, it is dried in the drying unit 18 and carried out from the main body 10. Development tank 12, bleach-fixing tank 1
4, washing tanks 16a to 16e, drainer 17, dryer 18
Is provided with a pair of transport rollers 24 that sandwich the photosensitive material 20 and transport each processing section. The transport roller pair 24 in the water draining section 17 also serves as a water removing roller having a function of removing water droplets on the photosensitive material 20 by squeezing, absorbing, or the like. The photosensitive material 20 is subjected to color development processing by being dipped in the processing liquid for a predetermined time while being nipped and carried by the carrying roller pair 24 with the emulsion surface facing down. Wash tank 16
Five tanks a to 16e are arranged, and each tank is cascade-piped, and the cleanliness of the rinsing water gradually decreases from the last-stage tank 16e to the front-most tank 16a. The water washing tank is equipped with a reverse osmosis membrane (RO membrane) device 26, and the water in the fourth water washing tank 16d is pressure-fed to the reverse osmosis membrane device 26 by the pump 28, so that the water permeates through the reverse osmosis membrane device 26 for clean permeation. The water is supplied to the fifth washing tank 16e, and the concentrated water that has not permeated the reverse osmosis membrane device 26 is supplied to the fourth washing tank 16d. Drying section 1
A fan 30 for sending warm air is provided below 8.
The warm air generated by the fan 30 is supplied to the drying unit 18 through the slit 32, and the photosensitive material 20 is dried.

FIG. 2 is a configuration diagram of the washing tank. Wash tank 16
a to 16e are cascaded, and the fourth washing tank 1
The 6d and the fifth washing tank 16e are connected to the reverse osmosis membrane device 26. Then, the photosensitive material 20 is designed to be conveyed from the water without going out into the air. Each washing tank 16a ~
16e is provided with a processing roller 54 which rotates in contact with the emulsion surface of the light-sensitive material 20 in water. The light-sensitive material 20 is processed by being supplied with water by the processing roller 54 while being conveyed in water. . The absolute value of the peripheral speed of the processing roller 54 is 1.5 times or more the absolute value of the photosensitive material conveying speed, and the rotational direction may be either direction. The peripheral surface of the processing roller 54 preferably has irregularities such as a spiral groove, a groove along the axial direction, and a groove along the circumferential direction. Shutter means 56 is provided between the adjacent washing tanks so as to allow the photosensitive material 20 to pass therethrough and prevent movement of the washing water. Shutter means 56
Is a blade shutter including, for example, a pair of flexible blades, and the tip end portion is elastically brought into close contact with the blade shutter. The opening ratio of the water washing tanks 16a to 16e is preferably 0.001 or less. Here, the definition of the opening ratio is a value obtained by dividing the surface area of the washing tanks 16a to 16e by the volume of the washing tanks 16a to 16e.

FIG. 3 is a structural view of another embodiment of the washing tank.
The water washing tanks 16a to 16e are cascaded in the same manner as in the above-mentioned configuration, and the photosensitive material 20 is conveyed from the water without going out into the air. Similar to the above, shutter means 5 such as a blade shutter is provided between the adjacent washing tanks.
6 is provided. The main washing tank is different from that shown in FIG. 2 in that a pair of conveying rollers 24 is provided in water, and the photosensitive material 20 is squeezed by a shutter means 56 which is a blade shutter after coming into contact with the washing water. It is processed well.

FIG. 4 is a block diagram of the shutter means 56. A slit 62 is formed in the tank wall 60 of the washing tank, and the shutter means 56 is provided so as to close the slit 62. The shutter means 56 is a pair of flexible blades 5.
The blade shutter is composed of 8 and has one end fixed to the tank wall 60 and the other end elastically closely contacting to close the slit 62. The photosensitive material 20 receives the driving force and is pushed between the blades 58 in the right direction in the drawing so that the photosensitive material 20 can pass between the blades 58. Even when the photosensitive material 20 passes, the blade 58 is in close contact with the photosensitive material 20. ,
Rinsing water between the tanks does not move through the slit 62.

FIG. 5 is a block diagram of another mode of the shutter means 56. This shutter means 56 is composed of one flexible blade 58, and one end thereof is fixed to the tank wall 60 so as to close the slit 62 formed in the tank wall 60. The other end of the blade 58 elastically comes into close contact with the tank wall 60a in the slit 62 to close the slit 62. Photosensitive material 20
Is capable of passing through the slit 62 by receiving a driving force and being pushed between the blade 58 and the tank wall 60, and the tank wall 60 and the blade 58 are in close contact with the photosensitive material 20 even when the photosensitive material 20 passes therethrough. Therefore, the wash water between the tanks does not move through the slit 62. In the case of this shutter structure, it is preferable that the emulsion surface of the light-sensitive material 20 is in contact with the blade 58.

[0078]

According to the present invention, since the light-sensitive material is washed and / or stabilized in a multi-stage countercurrent bath without contacting with air, good processing can be performed without an increase in stain. Further, even if the fixing agent contains at least one of a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound, the fixing agent or the silver salt does not adhere to the roller or the like that conveys the photosensitive material. Since the frequency of cleaning is reduced, maintenance is easy.

[0079]

【Example】

Example 1 Preparation of Sample 1 After a corona discharge treatment was applied to the surface of a paper support that was screen-laminated with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to form a sample 1. A multi-layer color photographic paper (Sample 1) having the layer constitution shown in was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for fifth layer Cyan coupler (Exc) 32.0 g, color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-
8) To 5.0 g, 50.0 cc of ethyl acetate and 14.0 g of a solvent (Solv-6) were added and dissolved, and this solution containing 8 cc of sodium dodecylbenzenesulfonate was added.
After adding to 500 cc of 0% gelatin aqueous solution, it was emulsified and dispersed by an ultrasonic homogenizer to prepare an emulsified dispersion. On the other hand, silver chlorobromide emulsion (cubic, average grain size of 0.
1: 4 mixture of 58 μm large size emulsion and 0.45 μm small size emulsion (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and in each size emulsion, 0.6 mol% of silver bromide was locally contained in a part of the grain surface. This emulsion contains the red sensitizing dye E shown below.
Is 0.9 × 1 for large size emulsions per mole of silver.
0 ^-4 mol, or 1.1 x 10 for small size emulsions
^-4 mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

The coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, the total amount of Cpd-10 and Cpd-11 in each layer is 2
It was added to a 5.0 mg / m ² and 50.0 mg / m ^2. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. That is, the sensitizing dye A and the sensitizing dye B are added to the blue-sensitive emulsion layer per mol of silver halide in an amount of 2.0 × 10 ⁻⁴ mol for a large-sized emulsion and each for a small-sized emulsion. 2.5 × 10 ⁻⁴ mol

[0082]

[Chemical 18]

Sensitizing dye C was added to the green-sensitive emulsion layer per mol of silver halide, and 4.0 × 10 ⁻⁴ for a large-sized emulsion.
5.6 × 10 ⁻⁴ mol for small size emulsion and 7.0 × 10 ⁻⁵ mol for small size emulsion with sensitizing dye D per mol of silver halide as small size emulsion. For 1.0 x 10 ^-5 mol,

[0084]

[Chemical 19]

Sensitizing dye E was added to the red-sensitive emulsion layer per mol of silver halide, and 0.9 × 10 ⁻⁴ for large-sized emulsion.
1.1 × 10 ⁻⁴ mol was added to each of the small and small size emulsions.

[0086]

[Chemical 20]

Furthermore, the following compound H was added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0088]

[Chemical 21]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-mercaptotetrazole with silver halide 1
8.5 × 10 ⁻⁵ moles, 7.7 × 10 ⁻⁴ moles per mole,
2.5 × 10 ⁻⁴ mol was added. Also, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0090]

[Chemical formula 22]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0 3: 8 mixture of large size emulsion of 0.88 μm and small size of 0.70 μm (molar ratio of silver), coefficient of variation of grain size distribution is 0.88 and 0.10, respectively, and bromide for each size emulsion Silver 0.3 mol% was locally contained in a part of the grain surface) 0.25 Gelatin 1.09 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv- 3) 0.15 solvent (Solv-7) 0.15 color image stabilizer (Cpd-7) 0.06 second layer (color mixing preventing layer) gelatin 1.00 color mixing preventing agent (Cpd-5) 0.08 solvent (Solv-1) 0.11 solvent (S lv-4) 0.05

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion with average grain size 0.55 μm and small size emulsion with 0.39 μm (silver mole ratio)) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of AgBr was locally contained in a part of the grain surface.) 0.12 Gelatin 1.15 Magenta coupler (ExM ) 0.17 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-3) 0.16 color image stabilizer (Cpd-4) 0.02 color image stabilizer (Cpd-9) 0 .02 solvent (Solv-2) 0.32 fourth layer (ultraviolet absorbing layer) gelatin 1.30 ultraviolet absorber (UV-1) 0.47 color mixing inhibitor (Cpd-5) 0.05 solvent (Solv-5) ) 0.19

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having average grain size 0.58 μm and small size emulsion 0.45 μm (silver mole ratio)) The coefficient of variation of the grain size distribution is 0.09 and 0.11, and AgBr 0.6 mol% was locally contained in a part of the grain in each size emulsion.) 0.20 Gelatin 0.91 Cyan coupler (ExC) 0.35 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth Layer (UV Absorbing Layer) Gelatin 0.40 UV Absorbing Agent (UV-1) 0.16 Color Mixing Preventing Agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh Layer ( Protective Layer) Gelatin 1.00 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.17 Liquid paraffin 0.03 Specific contents of the compound in each of the above layers are shown below.

[0095]

[Chemical formula 23]

[0096]

[Chemical formula 24]

[0097]

[Chemical 25]

[0098]

[Chemical formula 26]

[0099]

[Chemical 27]

[0100]

[Chemical 28]

[0101]

[Chemical 29]

[0102]

[Chemical 30]

After cutting the samples prepared as described above, a sensitometer (manufactured by Fuji Photo Film Co., Ltd.) FW type,
A light source color temperature of 3200 ° K) was used to provide a gradation exposure of a three color separation filter for sensitometry. After exposure, processing was performed in the following processing steps. After that, a sample exposed to white light was prepared, and the same treatment process was performed.

Treatment process Temperature Time Replenishment amount * Tank capacity Color development 40 ° C. 20 seconds 2 liters below Bleach fixing 40 ° C. 15 seconds 35 ml 2 liters Rinse 40 ° C. 5 seconds ―― 1 liter rinse 40 ° C. 5 seconds ―― 1 liter rinse 40 ℃ 5 seconds ----- 1 liter rinse 40 ℃ 5 seconds ----- 1 liter rinse 40 ℃ 5 seconds 60 ml 1 liter dry 60-80 ℃ 15 seconds * Replenishment amount per 1 m ² of photosensitive material (5 tank countercurrent to rinse → The rinse water was pumped to the reverse osmosis membrane, the permeate was supplied to the rinse, and the concentrated water that did not permeate the reverse osmosis membrane was returned to the rinse for use. The composition of each treatment liquid is as follows. The color developing solution was composed of two replenishing solutions, which were replenished so as not to be mixed at the same time.

Color Developer [First Replenisher] N-Ethyl-N- (β-methanesulfonamidoethyl) -9.5 g 3-Methyl-4-aminoaniline / 3/2 sulfate / 1 hydrate Sulfinate (S-5) 0.4 g Sodium sulfite 0.06 g 1,2-dihydroxybenzene-4,6 disulfonic acid 2 na 0.5 g Thorium water was added to 100 ml pH (25 ° C.) 3.5 [ Second Replenisher] Triethanolamine disodium-N, N-bis (sulfonate ethyl) hydride 4.6 g Roxylamine triisopropylnaphthalene (β) sodium sulfonate 0.1 g Ethylenediaminetetraacetic acid 2.0 g Fluorescent brightening Agent (UVITEX CK, manufactured by Ciba Geigy) 0.5 g Potassium carbonate 16.0 g Water was added to 200 ml pH (25 ° C.) 13.4

Color developing solution (tank solution) First replenisher 100 ml Second replenisher 200 ml Potassium carbonate 15 g KCl 10 g KBr 0.03 g Water was added 1000 ml pH (25 ° C.) 10.35

[0107] The first replenisher replenishing amount 12.4 ml (1 m per ²⁾ Replenishment rate 20.0 ml (1 m per ²⁾ of the second replenisher Bleach-fixing solution Tank solution Water 500ml fixing agent (see Table 6) 0.5 Molar ammonium sulfite 40 g (Used only when the fixing agent is ammonium thiosulfate) Ethylenediaminetetraacetic acid iron (III) ammonium 77 g Disodium ethylenediaminetetraacetate 5 g Ammonium chloride 42 g Acetic acid (50%) 116 ml Water added 1000 ml pH ( 25 ° C.) (adjusted with acetic acid and ammonia water) 4.7 (The composition of the replenisher is the same except that the pH of the tank solution is set to 4.0.)

Rinsing solution Ion-exchanged water (3 ppm each for calcium and magnesium)
[Evaluation of desilvering performance] The amount of residual silver was measured using a fluorescent X-ray analyzer with respect to the white exposed film of the post-treated sample. [Evaluation of Image Temporal Stain] The post-treatment sample (imagewise exposed film) was stored for 7 days in a thermo-hygrostat controlled to 70% at 60 ° C., and then the minimum density of yellow of the sample was measured. . The increase in yellow density before and after storage was represented by ΔD _min . [Evaluation of Image Density] With respect to the post-treatment processed sample (imagewise exposed film), the maximum density (D) of cyan was measured using a photographic densitometer FSD103 manufactured by Fuji Photo Film Co., Ltd.
_max ) was measured. Further, the stain level of the processed sample (Fr) was visually examined. The evaluation was decided based on the following criteria. Almost none: ○, Partially seen: △, Present on the entire surface of the image: × [Evaluation of solution stability] The rinse solution after running and after standing was visually examined for the degree of turbidity. The evaluation was decided based on the following criteria. No suspended matter: ○, Small amount of suspended matter: △, Large amount of suspended matter: ×

In the running process, the replenishment amount of the bleach-fixing solution is
Continuous treatment was performed until the tank capacity was doubled. Then 7
The performance and the condition of the rinse solution of the sample which was left for one day without treatment and then retreated was observed. The rinse liquid is a submerged blade method (II) in which a multi-stage countercurrent washing bath having blades in a bath as shown in FIG. 3 is used, and a conventional roller shown in FIG. Transport method
(I) was carried out. FIG. 6 is a block diagram showing a conventional conveying system, in which the photosensitive material 20 is conveyed by a conveying roller 24.
Are alternately transported in water and in the air. Further, a conventional ATS was used in place of the fixing agent of the present invention, and the processing was performed to make a comparative example. The results are shown in Table 6.

[0110]

[Table 6]

As can be seen from Table 6, according to the present invention, even after bleach-fixing and washing with water for a short time, there is no desilvering property, no Fr and no stain after aging, and the stability of the rinse solution is good. It turns out that various results are obtained. Further, according to the present invention, the blade portion is less contaminated with deposits and the like, so that cleaning of the blade is unnecessary. On the other hand, in the conventional method using the ATS, the suspended matter adhered to the blade portion and the cleaning frequency was high.

Example 2 Example 1 was repeated except that the light-sensitive material used in Example 1 was used and the color developing process and washing method were changed as described later.
The same test was performed. Treatment process Temperature Time Replenishment amount * Tank capacity Color development 40 ° C 15 seconds 35ml 2 liters Bleach fixing 40 ° C 15 seconds 35ml 2 liters Rinse 40 ° C 5 seconds ----- 1 liter Rinse 40 ° C 5 seconds ----- 1 liter rinse 40 ° C 5 Second--1 liter Dry 60-80 ° C 15 seconds 120ml (Rinse → 3 tank countercurrent method) * Replenishment amount per 1 m ² of light-sensitive material

The rinse water is pumped to the reverse osmosis membrane,
The permeated water was supplied to the rinse, and the concentrated water that did not permeate was returned to the rinse for use. The color developing solution was the following developing solution, and the bleach-fixing solution used was the same as in Example 1. The processing method is the conventional roller transfer method (I) used in the first embodiment.
In addition to the submerged blade method (II), a method using a submerged blade and a processing roller having the configuration shown in FIG. 2 was carried out. The photosensitive material conveying speed is 1.4 cm / sec, the processing roller diameter is 3 cm, the rotation speed is 750 rpm, and the surface shape of the processing roller is a spiral of 2 mm pitch inclined by 10 ° with respect to the photosensitive material conveying direction.

Color developer tank liquid replenisher water 700 ml 700 ml ethylenediaminetetraacetic acid 1.5 g 3.75 g 1,2-dihydroxybenzene-4,6 0.25 g 0.7 g disodium disulfonate triethanolamine 5.8 g 14.5 g potassium chloride 10.0 g --- potassium bromide 0.03 g --- potassium carbonate 30.0 g 39.0 g sodium hydrogen carbonate 5.3 g --- optical brightener 2.5 g 5.0 g (UVITEX CK, manufactured by Ciba Geigy) Sodium sulfite 0.14 g 0.2 g disodium-N, N-bis (sulfonate 7.4 g 18.5 g ethyl) hydroxylamine 4-amino-3 -Methyl-N-ethyl-N-1 13.1 g 33.0 g (4 hydroxybutyl) aniline.2 p-toluenesulfonic acid Was added 1000ml 1000ml pH (25 ℃) 10.05 11.60

The fixing agents in the bleach-fixing solution are as shown in Table 7. The results of Example 2 are shown in Table 7.

[0116]

[Table 7]

From the results shown in Table 7, the treatment (I
I) and (III) have better desilvering properties than the conventional treatment (I),
It can be seen that the Fr stain and the stain over time are small, and the stability of the rinse liquid is good. It was also found that the time-dependent stain can be further reduced by combining the submerged blade of the treatment (III) and the treatment roller.

Example 3 The same process as in Example 1 was performed except that the photosensitive material 2 described below was used instead of the photosensitive material used in Example 1 and the exposure method was described below. The rinse is shown in Fig. 3.
The submerged blade method shown in FIG. (Preparation of emulsion a) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (2% aqueous solution) was added. An aqueous solution containing 0.2 mol of silver nitrate in this aqueous solution,
0.2 mol sodium chloride and 15μ rhodium trichloride
An aqueous solution containing g was added and mixed at 56 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.780 mol of silver nitrate and an aqueous solution containing 0.780 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were added and mixed at 56 ° C. with vigorous stirring. Five minutes after the addition of the silver nitrate aqueous solution and the alkali halide aqueous solution was completed, an aqueous solution containing 0.020 mol of silver nitrate was further added, and potassium bromide 0.01
An aqueous solution containing 5 mol, 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridium (IV) ate was added and mixed at 40 ° C. with vigorous stirring. Then, a copolymer of isobutene maleic acid 1-sodium salt was added, and the mixture was washed by sedimentation and desalting. Furthermore, 90.0 g of lime-processed gelatin was added to adjust the pH of the emulsion and pAg.
Were prepared to 6.2 and 6.5, respectively. Further, sulfur sensitizer (triethylthiourea) 1 × 10 ⁻⁵ mol / molAg
And chloroauric acid 1 × 10 ⁻⁵ mol / mol Ag and nucleic acid 0.2
g / molAg was added, and optimal chemical sensitization was performed at 50 ° C.

With respect to the obtained silver chlorobromide (a), the particle shape, particle size and particle size distribution were determined from electron micrographs. All of these silver halide grains are cubic and have a grain size of 0.52 μm and a coefficient of variation of 0.
It was 08. The particle size is represented by the average value of the diameter of the circle equivalent to the projected area of the particle, and the particle size distribution is the standard deviation of the particle size divided by the average particle size. The halogen composition of the emulsion grains was then determined by measuring the X-ray diffraction from the silver halide crystals. The diffraction angle from the (200) plane was measured in detail using a monochromatic Cukα ray as a radiation source. A diffraction line from a crystal having a uniform halogen composition gives a single peak, whereas a diffraction line from a crystal having a localized phase having a different composition gives a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the diffraction angle of the measured peak, the halogen composition of silver halide constituting the crystal can be determined. The measurement results of this silver chlorobromide emulsion (a) were centered at 70% silver chloride (30% silver bromide) in addition to the main peak at 100% silver chloride, and 60% silver chloride (40% silver bromide). I was able to observe a broad diffraction pattern with the hem stretched to around.

(Preparation of Photosensitive Material 2) After corona discharge treatment was applied to the surface of a paper support screen-laminated with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper having the following layer structure was prepared.
The coating liquid was prepared as follows. Preparation of coating liquid for the first layer Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-)
7) 0.7 g of ethyl acetate 27.2 cc and solvent (S
Olv-3) and (Solv-7) are 4.1.
g and dissolved, and this solution was added with 10% sodium dodecylbenzenesulfonate 8cc 10% gelatin aqueous solution 1
Emulsified and dispersed in 85 cc to prepare an emulsified dispersion. On the other hand, in the silver chlorobromide emulsion (a), the following red-sensitive sensitizing dye (Dy
An emulsion containing e-1) was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1-oxy-3,5-dichloro-s.
-Triazine sodium salt was used. In addition, Cp for each layer
The total amount of each of d-10 and Cpd-11 is 25.0 mg.
/ M ² and 50.0 mg / m ² were added. The following were used as the spectral sensitizing dye for each layer.

[0121]

[Chemical 31]

[0122]

[Chemical 32]

[0123]

[Chemical 33]

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the yellow color-forming emulsion layer, the magenta color-forming emulsion layer and the cyan color-forming emulsion layer in an amount of 8.0 × 10 ^-4 per mol of silver halide. Mol added. The following dyes were added to the emulsion layer to prevent irradiation.

[0125]

[Chemical 34]

[0126]

[Chemical 35]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)] First layer (red sensitive yellow color forming layer) The silver chlorobromide emulsion (a) 0. 30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-) 7) 0.06

Second Layer (Color Mixing Prevention Layer) Gelatin 0.64 Color mixing inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third Layer (Infrared-sensitive Magenta Coloring Layer) Silver Chlorobromide Emulsion (a) 0.12 Gelatin 1.28 Magenta Coupler (ExM) 0.23 Color Image Stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (UV light Absorption layer) Gelatin 1.41 Ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth layer (infrared-sensitive cyan color-forming layer) Silver chlorobromide emulsion (a) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent ( Solv-6) 0.14 Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.10 Polyvinyl alcohol acryl-modified copolymer (modification degree 17%) 0.17 Liquid paraffin 0.03

The specific contents of the compound in each of the above layers are the same as those shown in Example 1. The fixing agents in the bleach-fixing solution are as shown in Table 8. Semiconductor laser AlG
aInP (oscillation wavelength, about 670 nm), semiconductor laser GaAlAs (oscillation wavelength, about 750 nm), GaAlA
s (oscillation wavelength, about 830 nm) was used. The laser light is a device capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron. Using this device, the light amount is changed to change the relationship between the density (D) of the photosensitive material and the light amount (E) D-logE
I asked. The light quantity of the semiconductor laser was controlled by combining a pulse width modulation method that modulates the light quantity by changing the energization time to the semiconductor laser and an intensity modulation method that modifies the light quantity by changing the energization quantity. This scanning exposure is 40
The average exposure time per pixel at this time was about 10 ^-7 seconds. The results of Example 3 are shown in Table 8.

[0132]

[Table 8]

From the results shown in Table 8, the submerged blade method (I
In I), when the fixing agent of the present invention is used, the desilvering property is extremely good as compared with the case where the conventional ATS is used.
Less r-stain and time-dependent stain, good stability of rinse solution, and good results in all cases were obtained.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a processing apparatus that is an embodiment of the present invention.

FIG. 2 is a configuration diagram of a washing tank which is an embodiment of the present invention.

FIG. 3 is a configuration diagram of a modification of the washing tank.

FIG. 4 is a configuration diagram of shutter means.

FIG. 5 is a configuration diagram of a modified example of the shutter unit.

FIG. 6 is a schematic configuration diagram of a conventional washing tank.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 processing apparatus 12 developing tank 14 bleach-fixing tank 16 water washing tank 17 draining section 17 drying section 20 photosensitive material 24 conveying roller pair 26 reverse osmosis membrane apparatus 28 pump 30 fan 32 slit 54 processing roller 56 shutter means 58 blade 60 tank wall 62 slit

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G03D 13/00 7810-2H

Claims (4)

[Claims] 1. A method for subjecting a photographic light-sensitive material having at least one layer of a photosensitive silver halide emulsion on a support to exposure and development processing. A nitrogen-containing heterocycle having a sulfide group as a fixing agent after development. Compound, a mesoionic compound or a thioether compound containing at least one compound having a fixing ability, and thereafter, the photosensitive material is washed and / or stabilized by a multi-stage countercurrent bath without contact with air. Method for processing photographic light-sensitive material. 2. The silver halide emulsion has a silver chloride content of 90.
2. The composition according to claim 1, wherein the particles contain mol% or more.
The method for processing a photographic light-sensitive material described in. 3. The photosensitive material is brought into contact with the peripheral surface of a processing roller provided in the processing liquid of the multi-stage countercurrent bath, and the absolute value of the peripheral speed of the processing roller is larger than the absolute value of the photosensitive material conveying speed. 3. The method for processing a photographic light-sensitive material according to claim 1, wherein the processing roller is rotated at 75 rpm or more for processing. 4. The method for processing a photographic light-sensitive material according to claim 1, wherein the bath for washing and / or stabilizing treatment has an opening ratio of 0.001 or less.