JP2756519B2 - Processing of photographic light-sensitive materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material. It is about the method.

[0002]

2. Description of the Related Art In general, processing of a silver halide color photographic light-sensitive material comprises a color developing process and a silver removing process. In the silver removing process, the developed silver generated in the color developing process is oxidized (bleached) to a silver salt by a bleaching agent having an oxidizing effect, and further removed from the photosensitive layer by a fixing agent that forms soluble silver together with unused silver halide. (Fixation). A ferric (III) ion complex salt (for example, aminopolycarboxylic acid-iron (III) complex salt) is mainly used as a bleaching agent, and a thiosulfate is generally used as a fixing agent. Bleaching and fixing are performed as independent bleaching and fixing steps, respectively.
It may be performed simultaneously as a bleach-fixing step. Details of these processing steps can be found in James' 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 developing machine. In particular, in recent years, small automatic developing machines called minilabs have been installed in stores, and rapid processing services have been widely spread to customers.
The bleaching agent and the fixing agent are used in the same bath as a bleach-fixing bath in color paper processing 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 processing steps and easiness of maintenance, and also for bleaching / fixing steps, drastic speeding up and improvement of liquid stability have been desired. Furthermore, the problem of processing waste liquid has increased as processing has been performed in various places.

[0003] In the bleaching step, a ferric ethylenediaminetetraacetic acid complex salt has conventionally been used. In addition, red blood salts and iron chlorides are known as bleaching agents which have strong oxidizing power and achieve rapid bleaching. It cannot be widely used due to inconvenience in handling such as corrosion. Recently, a ferric 1,3-diaminopropanetetraacetic acid complex salt has been proposed as a bleaching agent having rapid bleaching properties and versatility. However, this bleaching agent is liable to cause bleaching fog due to bleaching, and is not sufficient as a bleaching agent. On the other hand, thiosulfate used as a fixing agent,
Sulfite is added as an antioxidant preservative in most cases because it undergoes oxidative degradation to sulfide and precipitate. However, as the replenishment is further reduced, the improvement of the liquid stability is further desired.However, in the case where the sulfite is added in an increased amount, the solubility problem and the precipitation of sodium sulfate occur when the sulfite is oxidized. , Is no longer solved. Further, the lower the pH of the solution, the greater these problems.
Also, from the viewpoint of speeding up, compounds having better fixing properties than thiosulfates are desired.

When rapid bleach-fixing processing is performed after rapid color development, sensitizing dyes used in developing agents and photosensitive materials, which have been conventionally removed in the bleach-fixing step, do not sufficiently remove dyes and the like. For this reason, stains have come to appear on the processed image. Therefore, development of a fixing agent and a bleaching agent which solves the above problems, and a processing composition and a processing method using the same have been strongly desired. In view of such a problem, the present inventors have studied various fixing agents having excellent oxidation stability in place of thiosulfate. As a result, at least one of a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound is considered. By using a bleach-fixing solution containing the compound, it is stable against oxidation and has no precipitation even at a low replenishing rate. It has been found that good results can be obtained with the bleach-fixing agent.

[0005]

However, in the short processing time of bleach-fixing, as described above, the removal of the color developing agent, sensitizing dyes and dyes brought in from the color developing bath is insufficient, so that all the processing steps are performed. , The shorter the bleach-fix processing time, the more difficult it becomes. In particular, the removal of the developing agent is a serious problem, and if the bleach-fixing time and the washing or stabilizing time are shortened, stains are markedly formed on the image, and the adverse effect is observed. It has been found that the lower the pH of the bleach-fix bath is, the better the removal of the developing agent is, and it is preferable that the pH is 5 or less.

Further, when the treatment is performed using the above fixing agent,
It was found that the fixing agent and the silver salt adhered to the photosensitive material transporting roller during the light processing. Here, the idle processing refers to the following case. When the processing amount per day is short or the processing time is short. When the amount of processing per unit time during operation is small. When the interval between operations is long. For example, when the processing time in one operation is short (the processing amount is small) and the stop time is long for that, or when the operation time is long and the stop time until the next processing is long. If the fixing agent or the silver salt adheres to the conveying roller and becomes contaminated at the time of such a lightening process, these convey to the photosensitive material and become contaminated, so that the conveying roller needs to be cleaned frequently.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to provide a method of processing a photographic light-sensitive material capable of preventing stains and enabling ultra-rapid processing, and which does not cause stain on a roller for conveying the photographic light-sensitive material. To provide.

[0008]

The above object of the present invention is achieved by a processing method described in the following (1) to (4). (1) A method for exposing and developing a photographic material having at least one layer comprising a photosensitive silver halide emulsion on a support, comprising: after development, a nitrogen-containing heterocyclic compound having a sulfide group as a fixing agent; After treatment with a bath having a fixing ability containing at least one compound of a mesoionic compound or a thioether compound, washing and / or stabilizing treatment are carried out in a multi-stage countercurrent.
When performing in a bath, make sure that the photosensitive material does not come into contact with air.
A photographic light-sensitive material, which is moved in water to be washed and / or stabilized. (2) The silver halide emulsion contains 90 mol% of silver chloride.
The method for processing a photographic light-sensitive material according to the above (1) , comprising the above particles. (3) The photosensitive material is provided in contact with the peripheral surface of the processing roller in the processing liquid of the multi-stage countercurrent bath so that the absolute value of the peripheral speed of the processing roller is greater than the absolute value of the photosensitive material transport speed. The method according to the above (1) or (2) , wherein the processing is performed by rotating the processing roller at 75 rpm or more. (4) The opening ratio of the water washing and / or stabilizing processing bath is equal to or more than 0.001 (1) -
The method for processing a photographic light-sensitive material according to any one of (3) and (3) .

When the washing and / or stabilizing treatment is carried out in a multi-stage countercurrent bath, the photosensitive material moves between the tanks in water so as not to come into contact with air. Each photosensitive material can be moved underwater.
A photosensitive material passage is formed between the tanks, and the passage is opened and closed by shutter means. The shutter means can be constituted by providing a pair of flexible blades with only their leading ends elastically contacting each other. By moving the photosensitive material in the water between the washing baths, the generation of stain can be suppressed. By using a photosensitive material using a high silver chloride emulsion having no or little silver iodide and silver bromide, it is possible to prevent deposits on the transport roller and an increase in stain. By treating with a bath having a fixing ability containing at least one compound selected from a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound and a thioether compound as a fixing agent, stable treatment can be achieved even when the treatment is carried out and / or with low replenishment. Good sedimentation and no turbidity. In addition, the image stain is small even after washing with water for a short time, and the stain with time after long-term storage of the image is small. It is preferable that at least one of the nitrogen-containing heterocyclic compound, the mesoionic compound, and the thioether compound is contained in an amount of 0.1 mol / L or more. The processing solution in the present invention does not need to contain a sulfite, so that it becomes possible to squeeze or strongly agitate with a blade or the like in the water washing process, and to wash out unnecessary components (developing agent, dye, etc.) from the photosensitive material in a short time. It becomes possible.

The processing time according to the present invention is preferably within 25 seconds in the bleach-fixing step and within 120 seconds from the beginning of the developing step to the end of the drying step. In the bleach-fixing for a short time, a large amount of the developing agent accumulates in the light-sensitive material to cause stain, and it is difficult to sufficiently remove the silver salt. In particular, the tendency is large for p-phenylenediamine color developing agents. However, when the photosensitive material passes between the plates in the water, the unnecessary substances are easily removed. Further, the processing time can be further shortened by providing a rotating processing roller in the liquid and bringing the photosensitive material into contact with the peripheral surface of the processing roller for processing. The rotation speed of the processing roller is 75 rpm
m or more, and the rotation direction may be the same as or opposite to the photosensitive material transport direction. In the processing of the present invention, the bleach-fixing solution contains at least one metal chelate compound comprising compounds represented by the following general formulas (I), (II), (III), (IV) and (V). Is preferred. General formula (I)

[0011]

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In the formula, X represents —CO—N (OH) —R _a ,
N (OH) -CO- _Rb (where _Ra represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group; _Rb 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 represents a hydrogen atom, an aliphatic group, .R _f fat representing an aromatic group or a heterocyclic group Represents an aromatic group, an aromatic group or a heterocyclic group). L ₁ represents a divalent linking group including 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 represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. General formula (II)

[0013]

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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 ( where Y ₁ and Y ₂ have the same meanings as L ₁ in formula (I) .R _g, R _h and R _i have the general formula ( is synonymous with R _a of I) .R _j is a R _a aliphatic group, an aromatic group, a heterocyclic group, -NR _k (R _l) (wherein R _k and R _l have the general formula (I) Has the same meaning) or —OR _m (where 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]

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

[0017]

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In the formula, R ₄₁ and R ₄₂ represent R _{11 of the} 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]

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In the formula, L ₃ represents a divalent linking group including 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 may be the same or different and each represent 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,
Represents an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfinyl group. Also R
₅₈ and R ₅₉ may be linked to form a ring. t and u represent 0 or 1.

According to the present invention, rapid washing and / or stabilization treatment can be performed, and treatment for transporting the inside of the treatment bath can be performed. It is possible to perform a sufficiently satisfactory process even with a processing device having a small rate. Further, for the same reason, processing with a low replenishment rate is possible. The aperture 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 oxidization property 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 gives stain to an image can be quickly removed. However, at 40 ° C. or higher, water evaporation was extremely large, and the aperture ratio was preferably set to 0.001 or lower.

The present invention is a processing method aimed at rapid and simple processing, and a photosensitive material having an alkali consumption of 3.0 mmol / m ² or less can be preferably used. As described in JP-A-3-109549, the alkali consumption is determined by pulverizing a light-sensitive material using a support and crushing the light-sensitive material from pH6 to pH1.
Defines the required amount of alkali needed to raise to zero. As the bleach-fixing composition of the present invention, a bleach-fixing solution is generally used, but a replenisher, a supply kit (solution or adhesive) and the like are also meant. The replenisher may be replenished by being divided into two or more types. General formulas (I), (II), (III), (IV)
And / or specific examples of the compounds represented by (V) and their synthesis methods are described in Japanese Patent Application Nos. 2-127479 and 2-175.
Nos. 026, 2-196,972, 2-201,8
No. 46, 2-258, 539. Representative examples of the compounds represented by formulas (I), (II), (III), (IV) and / or (V) are shown below, but are not limited thereto.

[0023]

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[0024]

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[0025]

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[0026]

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As the central metal used in the metal chelate compound, for example, Fe (III), Mn (III), Co (III),
Rh (II), Rh (III), Au (III), Au (II), Ce (I
V). As the metal chelate compound, those isolated as a metal chelate compound may be used. Of course, in the present invention, the general formulas (I), (II), (III), (IV)
And / or a metal salt such as a ferric sulfate complex salt, a ferric chloride salt, a ferric nitrate salt, a ferric ammonium sulfate salt, a ferric phosphate salt, and the like, It may be used by reacting in a solution. General formulas (I), (II), (II
The compounds represented by (I), (IV) and / or (V) are used in a molar ratio of 1.0 or more to the metal ion. This ratio is preferably large when the stability of the metal chelate compound is low, and is usually 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]

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The nitrogen-containing heterocyclic compound having a sulfide group used in the present invention may be any one of Berichte der Deutschen Hemischen Gezerschaft (Berichte der Deu).
tschen Chemischen Gesellschaft) 28, 77 (189
5), JP-A-50-37436, JP-A-51-3231
No. 3,295,976, U.S. Pat. No. 3,37
No. 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), U.S. Pat. Nos. 2,585,388 and 2,541,
No. 924, Advances in Heterocyclic Chemistr
y) 9, 165 (1968), Organic Synthesis 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, 3,420,670, 2,271,229
No. 3,137,578 and 3,148,066
Nos. 3,511,663 and 3,060,028
No. 3,271,154, 3,251,691
Nos. 3,598,599 and 3,148,066
No., JP-B-43-4135, U.S. Pat. No. 3,615,6
No. 16, 3,420,664, 3,071,46
No. 5, 2,444,605, 2,444,606
No. 2,444,607, 2,935,404, and the like. Hereinafter, specific examples of the mesoionic compound of the present invention are shown, but the present invention is not limited thereto.

[0030]

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[0031]

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[0032] The mesoionic compound of the present invention can be prepared by the method described in 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);
87322, Berichte der Deutschen Che
mischen Gesellschaft) 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 Heterochemistry
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), 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). Hereinafter, specific examples of the thioether compound of the present invention are shown, but the present invention is not limited thereto.

[0033]

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[0034]

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The thioether compound of the present invention can be prepared by the method described in Journal of Organic Chemistry (J. Org.
m.) 30, 2867 (1965), 27, 2846
(1962), Journal of American Chemical Society (J. Am. Chem. Soc.) 69, 2330.
(1947) can be easily synthesized.

The color photographic paper in the color photographic light-sensitive material used in the present invention comprises at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. It can be formed by coating. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. The image forming system including the light-sensitive material and processing which can be used in the present invention can be used for rapid processing of commonly used color prints, but can be used for intelligent color hard copy applications where speeding is more desired. In particular, as an aspect of the intelligent color hard copy, an aspect in which scanning exposure is performed using 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 a light-sensitive material used therefor can use an infrared-sensitive silver halide emulsion layer instead of at least one of the above emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

Further, depending on the required image quality and quality, the color coupler may be of two colors. In this case, the corresponding silver halide emulsion layers may be two layers. In this case, a full-color image is not obtained, but an image can be formed more quickly. As the silver halide emulsion used in the 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. However, when 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, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

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 for the purpose of minimizing a decrease in sensitivity when the light-sensitive material is subjected to pressure, the distribution of the halogen composition in the grains is reduced. 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 in order to reduce the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 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 defined by the diameter of a circle equivalent to the projected area of the grain, and the number average is taken) is preferably from 0.1 μm to 2 μm. . In addition, their particle size distribution is the coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size).
%, Preferably 15% or less, so-called monodispersed one. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral or octahedral, or an irregular shape such as spherical or tabular. ) Those having a crystal form or those having a composite form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, the particles having the above regular crystal form
The content is preferably 50% or more, preferably 70% or more, more preferably 90% or more.

In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter in circle / thickness in circle) of 5 or more, preferably 8 or more, exceed 50% of all grains as a projected area are preferably used. it can. In the photosensitive material according to the present invention, a dye capable of being decolorized by a treatment described in European Patent EP 0,337,490A2, pp. 27-76, is coated on a hydrophilic colloid layer for the purpose of improving image sharpness and the like. Among them, oxonol dyes are added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, and dihydric alcohols (for example, trimethylolethane) are added to the water-resistant resin layer of the support. ) Or the like is preferably contained in an amount of 12% by weight or more (more preferably 14% by weight or more). Further, in the photographic material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred. That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

The light-sensitive material according to the present invention is provided with a protective agent such as that described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add a fungicide. Further, as the support used in the light-sensitive material according to the present invention, a white polyester-based support for a display or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used. May be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. 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 photosensitive 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. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred. Also, upon exposure, U.S. Pat.
It is preferred to use the band stop filter described in 880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to color development processing, but it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Particularly when the 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 accelerating 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 processing applied to process this light-sensitive material As additives, the following patent publications, particularly European Patent EP 0,355,660A2 (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, the 3-hydroxypyridine-based cyan couplers described in European Patent EP 0,333,185 A2 (among the couplers (42) listed above as specific examples) 4-equivalent couplers obtained by adding a chlorine leaving group to a 2-equivalent coupler, couplers (6) and (9) are particularly preferred), and cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, However, coupler examples 3, 8 listed as specific examples,
3, 4 are particularly preferred). The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing, and washing (or stabilization). Bleaching and fixing may be performed separately, instead of in a single bath as described above.

In the present invention, known color developing agents are used. Representative examples 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, Illustrative Compound D is particularly preferred.
-3 and D-4. Such an active ingredient is effective in the replenishment method as in the present invention. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid and the like may be used. The amount of the aromatic primary amine developing agent used is preferably 1 liter per developer (as a tank solution).
0.002 mol to 0.2 mol, more preferably 0.005 mol to 0.1 mol. In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, “substantially free” means that the benzyl alcohol concentration is preferably 2 ml / l or less, more preferably 0.5 ml / l or less, and most preferably no benzyl alcohol is contained. It is more preferable that the developer or its replenisher used in the present invention does not substantially contain sulfite ions. Sulfite ions are
It has the function of dissolving silver halide and reacting with the oxidized developing agent to reduce the dye-forming efficiency simultaneously with the function as a preservative of the developing agent. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing. Here, "substantially not contained" means that the concentration of sulfite ions is preferably 0.10 mol or less per mol of the developing agent, and most preferably contains no sulfite ions. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before adjusting to a working 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 hydroxylamine itself has silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. As used herein, the term "substantially free of hydroxylamine" means preferably 5.0 × 10 ^-3 mol / mol.
It has a hydroxylamine concentration of less than one liter, and most preferably contains no hydroxylamine. The color developing solution and the replenisher thereof used in the present invention are:
It is more preferable to contain an organic preservative in place of the hydroxylamine and sulfite ions. Here, the organic preservative is added to the processing solution of the color photographic light-sensitive material,
Organic compounds that reduce the rate of degradation of aromatic primary amine color developing agents. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused amines, etc. It is an effective organic preservative. These are disclosed in JP-A-63-4235,
63-30845, 63-21647, 63-44655, 63-53551
Nos. 63-43140, 63-56654, 63-58346, 63
-43138, 63-146041, 63-44657, 63-44656
No. 3,615,503, U.S. Pat.
No. 52-143020 and Japanese Patent Publication No. 48-30496, etc.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
No. 588, salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat.
An aromatic polyhydroxy compound or the like described in the specification of JP-A No. 4 may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred. Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred. 1-18
No. 7557, etc. It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing.

The above amines include those described in JP-A-63-23944.
Cyclic amines as described in JP-A No. 7
Examples thereof include amines as described in JP-A-28340 and amines as described in JP-A-1-186939 and JP-A-1-187557. In the present invention, those represented by the following general formula (I) are preferably used as the hydroxylamine derivative. General formula (I)

[0052]

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(Wherein L represents an alkylene group which may be substituted, and A represents 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-substituted group. A good ammonio group, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl, or an alkylsulfonyl group which may be substituted, and R represents a hydrogen atom or an alkyl group which may be substituted.) Specific examples of the hydroxylamine derivative used in the present invention are described below, but are not limited thereto.

[0054]

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Hereinafter, specific examples of the sulfinic acid and salts thereof used in the present invention will be listed.

[0056]

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

In the present invention, the color developing solution preferably contains 0.5 × 10 ⁻⁵ mol / l to 1.0 × 10 ⁻³ mol / l. More preferably, 3.0
× 10 ^{-5 to} 5 × 10 ^-4 mol / l. When the bromine ion concentration is higher than 1 × 10 ^-3 mol / l, the development is delayed and the maximum concentration and sensitivity are reduced. When the bromide ion concentration is lower than 0.5 × 10 ^-5 mol / l, fog cannot be sufficiently prevented. . Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing. When directly added to the color developing solution, examples of the chloride ion supplying material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, and of these, preferred are Are sodium chloride and potassium chloride. Further, it may be supplied from a fluorescent brightener added to the developer. 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 are potassium bromide,
Sodium bromide.

When eluted from the photosensitive material during the development processing,
Both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources 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 further contain a compound of a known developing component. Above pH
It is preferable to use various buffering agents in order to maintain the pH. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N
-Dimethylglycine salt, leucine salt, norleucine salt,
Guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrate salts, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxyaminomethane salts, lysine salts, etc. Can be used. In particular, carbonates, phosphates, tetraborate, and hydroxybenzoate have high solubility, pH 9.0 or higher.
It is excellent in buffering capacity in the pH range, has the advantage that it has no adverse effect on photographic properties (such as fog) even when added to a color developing solution, and is inexpensive. It is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the invention is not limited to these compounds.
The amount of the buffer to be added to the color developer and its replenisher is 0.
It is preferably at least 1 mol / liter, especially 0.1 mol / l.
It is particularly preferred that it is from mol / l to 0.4 mol / l. In addition, various chelating agents can be used in the color developing solution as an inhibitor of precipitation of calcium or 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 hexane hexane diamine tetraacetic acid, 1,2-diaminopropane tetraacetic acid,
Glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic 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.

These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to block metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per liter. An optional development accelerator can be added to the color developer if necessary. As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9019 and U.S. Pat.No. 3,813,247, etc.
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, JP-B-44-30074, JP-A
Quaternary ammonium salts represented in JP-A-56-156826 and JP-A-52-43429, U.S. Patent Nos. 2,494,903 and 3,128,
No.182, No.4,230,796, No.3,253,919, JP-B-41-1
No. 1431, U.S. Pat.Nos. 2,482,546, 2,596,926, and 3,582,346, and the amine compounds described in each gazette or specification, Japanese Patent Publication Nos. 37-16088 and 42-25201,
No. 3,128,183, JP-B-41-11431, JP-B-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 as needed. 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 antifoggant include benzotriazole, 6-nitrohenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution applicable to the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, a 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. If necessary, polyvinyl alcohol, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, polyvinyl pyrrolidone, or various known water-soluble polymers of these copolymers, alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid And various surfactants such as aromatic carboxylic acid polyethylene oxide. The processing temperature of the color developing solution applicable to the present invention is 20 to 50C, preferably 30 to 45C. 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 appropriate.
Preferably it is 120 ml or less. More preferably 60 ml,
This 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 aperture ratio (air contact area (cm
² ) / volume of liquid (cm ³ )) is relatively superior to the combinations other than those of the present invention in any state, but from the viewpoint of the stability of the color developer, the liquid aperture ratio is 0 to 0.1.
cm ^-1 is preferred. In continuous processing, practically, it is 0.1.
The range is preferably 001 cm ^{-1 to} 0.05 cm ^-1 , and more preferably 0.002 to 0.03 cm ^-1 . Next, the desilvering step applicable to the present invention will be described. The desilvering step may be generally used in any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, a bleach-fixing step.

The bleaching solution, bleach-fixing solution and 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. In particular, organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolycarboxylic acids and the like) Complex salts such as phosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; and hydrogen peroxide. Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of processing at an hourly speed and preventing 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 any of sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-
Iron (II) of diaminopropanetetraacetic acid and methyliminodiacetic acid
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 or 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, phosphonocarboxylic acid, etc., to form a ferric ion complex salt in a solution. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylate iron complexes are preferable, and more preferably, a metal chelate compound comprising a compound represented by the general formula (I), (II), (III), (IV) or (V). It is preferable to contain at least one. The addition amount is 0.01 to 1.0 mol / l, preferably 0.05 to 0.50 mol / l.

Various compounds can be used as a bleaching accelerator in the bleaching solution, bleach-fixing solution and / or prebath thereof. For example, U.S. Pat. No. 3,893,858, German Patent 1,290,812, JP-A-53-95630, and 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.
And thiourea compounds described in the publications and specifications such as U.S. Pat. No. 3,706,561, and the like, or halides such as iodine and bromine ions are preferred in terms of excellent bleaching power. Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as an iodide (eg, ammonium iodide). If necessary, one or more inorganic acids having a pH buffering capacity 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, Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or the fixing solution includes a nitrogen-containing heterocyclic compound having a sulfide group,
It is a silver halide dissolving agent such as a mesoionic compound or a thioether compound, and 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 or more.
~ 2.0 moles. The pH range of the bleach-fixing solution or the fixing solution is preferably from 2 to 8, more preferably from 3 to 5. Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. The bleach-fixing solution and the fixing solution include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite It preferably contains a sulfite ion releasing compound such as (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of about 0.02 to 0.05 mol / l in terms of sulfite ion, more preferably 0.04 to 0.05 mol / l.
0.40 mol / liter. In addition, you may add ascorbic acid, a sulfinic acid carbonyl bisulfite adduct, or a carbonyl compound. Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide and the like may be added as required. The processing time of the bleach-fixing solution of the present invention is 5 seconds to 120 seconds, preferably 10 seconds to 60 seconds. The temperature is between 25 ° C and 60 ° C, preferably between 30 and 50 ° C. The replenishment amount is ²⁰ ml to 250 per m ² of photosensitive material.
ml, preferably 30 ml to 100 ml. After desilvering processing such as fixing or bleach-fixing, washing and / or stabilizing processing (hereinafter, unless otherwise specified, stabilizing processing is included in the water washing) is generally performed.

The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the purpose, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Usually, the number of stages in the multistage 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 per 1 m ^{2 of the} photosensitive material, and the effect of the present invention is remarkable. The increase in the residence time causes a problem that bacteria proliferate and the generated suspended matter adheres to the photosensitive material. Solutions to these problems include:
The method for reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based germicides such as chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-267761. A bactericide such as the benzotriazole or copper ion described can also be used. Furthermore,
As the aqueous water, a surfactant as a draining agent and a chelating agent represented by EDTA as a water softener can be used.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without 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 buffer for adjusting the membrane pH to a level suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used. Furthermore,
Surfactants, optical brighteners and hardeners can also be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, 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 water washed and / or stabilized may be treated with a reverse osmosis membrane. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, folivinylene carbonate, and the like can be used. Composite membranes are preferred.
Also, from the viewpoint of reducing the initial cost, running cost, downsizing, and noise reduction of the pump,
A low-pressure reverse osmosis membrane that can be used at a liquid sending pressure as low as kg / cm ² is preferable. Further, the structure of the membrane is preferably a spiral type in which a flat membrane called a spiral type is wound into a spiral shape because the amount of permeated water does not decrease.

The liquid sending pressure in the use of these membranes is in the range as described above, but the preferable conditions are ^{2 to} 10 kg / cm ² , and particularly preferably ^{3 to} 7 kg / cm ^{2 for} the effect of preventing stain and preventing the decrease in the amount of permeated water. it is cm ^2. The washing and / or stabilizing step is preferably connected to a multi-stage countercurrent system using 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 water in the second and subsequent tanks for such multistage countercurrent washing and / or stabilization. Specifically, the water in the second tank in the case of the two-tank configuration, the second or third tank in the case of the three-tank configuration, and the water in the third or fourth tank in the case of the four-tank configuration is treated with a reverse osmosis membrane and permeated. This is carried out by returning the water to the same tank (a tank from which water was collected for reverse osmosis membrane treatment; hereinafter, referred to as a collection tank) or a washing and / or stabilization tank located thereafter. Further, returning the concentrated washing and / or stabilizing solution to the bleach-fix bath upstream of the collection tank is one measure.

A chelating agent can be used in the washing bath of the present invention. Usable chelating agents can be selected from aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, alkylidene diphosphonic acids, metaphosphoric acids, pyrophosphoric acids, organic phosphonic acids or salts thereof, and polyphosphoric acids. it can. Especially Japanese Patent Application Hei 2-4
It is preferable to include an organic phosphonic acid compound described in No. 0940. The amount of these organic phosphonic acids and / or organic phosphonates to be added to the washing or stabilizing bath can be determined by the amount of ferric ethylenediaminetetraacetate contained in the photosensitive material. Bath 1
Preference is given to an addition amount of between 2.9 and 290 mmol per liter. More preferably, it is 14.6 mmol to 146 mmol. If the amount is too large, the surface may be sticky, while if it is too small, the original effect of improving stain cannot be obtained. It is also a preferred embodiment to use a magnesium or bismuth compound. In another preferred embodiment, a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound is used. A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment.

The preferred pH of the washing step or the stabilizing step is 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use, characteristics, etc. of the photosensitive material.
6060 ° C., preferably 35-50 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably it is 5 seconds to 45 seconds, more preferably 10 seconds to 35 seconds. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like. A specific preferable replenishing amount is 0.5 to 50 times, preferably 2 to 15 times the amount brought in from the previous bath per unit area of the photosensitive material. Alternatively, the amount is 300 ml or less, preferably 150 ml or less per m ^{2 of the} light-sensitive material. Replenishment may be performed continuously or intermittently. The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water is reduced by a multi-stage countercurrent method, and is allowed to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid. In the present invention,
In a washing water and / or a stabilizing liquid or any other processing liquid, a so-called jet jet can be performed. The jet can be generated by sucking the processing solution in the processing bath by a pump and discharging the processing solution toward the emulsion surface from a nozzle or a slit provided at a position facing the emulsion surface of the photosensitive material. More specifically, JP-A-62-183
No. 460, page 3, lower right column to page 4, lower right column, a method of discharging a liquid pumped by a pump from a slit or a nozzle provided opposite to the emulsion surface described in the section of Examples in the lower right column of page 4 can be adopted. . The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer to when it can form a final bath (generally a 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 and 30 seconds or less.

The drying step usable in the present invention will be described. In order to complete an image by the ultra-rapid processing of the present invention, a drying time of 20 to 40 seconds is desired. As a means for shortening the drying time, a means on the light-sensitive material side can be improved by reducing the amount of water taken into the film by reducing the amount of a hydrophilic binder such as gelatin. Also, from the viewpoint of reducing the amount of carry-in, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. Naturally, as a means for improving the dryer, it is possible to speed up the drying by increasing the temperature or increasing the drying air. further,
Drying can also be expedited by adjusting the irradiation angle of the drying air to the light-sensitive material or by removing the exhaust air.

[0072]

An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited only to this embodiment. FIG. 1 shows a silver halide photographic color paper processing machine to which the present invention is applied. This processor develops, bleach-fixes, exposes web-colored paper exposed based on positive documents.
After washing with water, it is dried to form an image on color paper. A color paper (hereinafter, referred to as a light-sensitive material) processed by the present 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. Color development is carried out with a color developer containing a primary amine color developing agent.

The processor 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 developed, bleach-fixed. After being washed with water, it is dried in the drying unit 18 and carried out of the main body 10. Development tank 12, bleach-fix tank 1
4, washing tanks 16a to 16e, draining unit 17, drying unit 18
Is provided with a transport roller pair 24 for transporting each processing section while holding the photosensitive material 20 therebetween. Further, the transport roller pair 24 in the draining unit 17 also functions as a water removing roller having a function of removing water droplets on the photosensitive material 20 by squeezing, absorbing, and the like. The photosensitive material 20 is color-developed by being immersed in a processing liquid for a predetermined time while being nipped and transported with the emulsion surface down by the transport roller pair 24. Wash tank 16
Five tanks a to 16e are arranged, and each tank is cascaded, and the cleanliness of the washing water is gradually reduced from the last tank 16e to the front tank 16a. The washing tank is provided with a reverse osmosis membrane (RO membrane) device 26, and the water in the fourth washing tank 16d is pumped to the reverse osmosis membrane device 26 by a pump 28, and clean water permeates through the reverse osmosis membrane device 26. The water is supplied to the fifth washing tank 16e, and the concentrated water that has not passed through the reverse osmosis membrane device 26 is supplied to the fourth washing tank 16d. Drying section 1
8, a fan 30 for sending warm air is provided.
The hot air generated by the fan 30 is supplied to the drying unit 18 through the slit 32, and dries the photosensitive material 20.

FIG. 2 is a structural view of the washing tank. Wash tank 16
a to 16e are cascaded, and the fourth washing tank 1
6d and the fifth washing tank 16e are connected to the reverse osmosis membrane device 26. The photosensitive material 20 is conveyed from underwater without going out into the air. Each washing tank 16a ~
16e, a processing roller 54 is provided which rotates in contact with the emulsion surface of the photosensitive material 20 in water. . The absolute value of the peripheral speed of the processing roller 54 is at least 1.5 times the absolute value of the photosensitive material transport speed, and the rotation 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 adjacent washing tanks so as to be able to pass through the photosensitive material 20 and to prevent movement of washing water. Shutter means 56
Is a blade shutter composed of, for example, a pair of flexible blades, and is provided with its tip portions elastically closely contacted. The opening ratio of the washing tanks 16a to 16e is preferably 0.001 or less. Here, the aperture ratio is defined as 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 configuration diagram of another embodiment of the washing tank.
The rinsing tanks 16a to 16e are cascaded similarly to the above configuration, and the photosensitive material 20 is conveyed from underwater to the air. A shutter means 5 such as a blade shutter is provided between the adjacent washing tanks as described above.
6 are provided. This washing tank differs from the structure shown in FIG. 2 in that the conveying roller pair 24 is provided in the water, and the photosensitive material 20 is squeezed by the shutter means 56 which is a blade shutter after coming into contact with the washing water. By doing so, it is processed well.

FIG. 4 is a diagram showing the construction 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 includes a pair of flexible blades 5.
8, one end of which is fixed to the tank wall 60 and the other end of which is elastically close to close the slit 62. The photosensitive material 20 can pass between the blades 58 by being pushed between the blades 58 to the right in the drawing under the driving force. ,
The washing water between the tanks does not move through the slit 62.

FIG. 5 is a structural view of another embodiment of the shutter means 56. The shutter means 56 is composed of one flexible blade 58 and has one end fixed to the tank wall 60 so as to close a slit 62 formed in the tank wall 60. The other end of the blade 58 elastically closely contacts the tank wall 60 a in the slit 62 to close the slit 62. Photosensitive material 20
Can be passed through the slit 62 by being pushed between the blade 58 and the tank wall 60 by receiving a driving force. Therefore, the washing water between the tanks does not move through the slit 62. In the case of this shutter configuration, it is preferable that the emulsion surface of the photosensitive material 20 is in contact with the blade 58.

[0078]

According to the present invention, the photosensitive material is washed and / or stabilized in a multi-stage countercurrent bath without contact with air, so that good processing can be performed without increasing the 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 and the silver salt do not adhere to a roller for transporting the photosensitive material. The maintenance is easy because the frequency of cleaning is reduced.

[0079]

【Example】

Example 1 Preparation of Sample 1 After a 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 applied. (Example 1) The coating solution was prepared as follows.

Preparation of Coating Solution for Fifth Layer 32.0 g of cyan coupler (Exc), 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.
After adding to 500 cc of 0% gelatin aqueous solution, the mixture was emulsified and dispersed with an ultrasonic homogenizer to prepare an emulsified dispersion. On the other hand, a silver chlorobromide emulsion (cubic, average grain size of 0. 1).
1: 4 mixture of 58 μm large size emulsion and 0.45 μm small size emulsion (Ag molar ratio). The variation coefficients of the grain size distribution were 0.09 and 0.11, and in each size emulsion, 0.6 mol% of silver bromide was locally contained in part of the grain surface. This emulsion has a red-sensitive sensitizing dye E shown below.
Is 0.9 × 1 for large emulsions per mole of silver.
^0-4 moles, and for small size emulsions 1.1 × 10
^-4 mol is added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion and the red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the following composition.

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

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Sensitizing dye C was added to the green emulsion layer per mole of silver halide, and 4.0 × 10 ^-4 for the large emulsion.
Mole, 5.6 × 10 ^-4 mole for small-size emulsion, and 7.0 × 10 ^-5 mole for small-size emulsion, and 7.0 × 10 ^-5 mole for small-size emulsion per mole of silver halide. 1.0 × 10 ^-5 mol,

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

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Further, 2.6 × 10 ^-3 mol of the following compound H was added per 1 mol of silver halide.

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The blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ⁻⁵ mol, 7.7 × 10 ⁻⁴ mol per mol,
2.5 × 10 ^-4 mol was added. In addition, 4-hydroxy-6-methyl-1, 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. The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (cube, average particle size 0) 3: 7 mixture (larger silver ratio) of a large size emulsion of 0.88 μm and a small size emulsion of 0.70 μm, the coefficient of variation of the grain size distribution is 0.88 and 0.10, respectively, and bromide is brominated in each size emulsion. 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 mixture prevention layer) Gelatin 1.00 Color mixture inhibitor (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 having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (silver molar ratio)) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface in each emulsion. 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 absorbing agent (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 an average grain size of 0.58 μm and small-size emulsion of 0.45 μm (silver molar ratio)) The coefficient of variation of the grain size distribution was 0.09 and 0.11, and each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface.) 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 (ultraviolet ray absorbing layer) Gelatin 0.40 Ultraviolet ray absorbing agent (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer ( Protective layer) Gelatin 1.00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification: 17%) 0.17 Liquid paraffin 0.03 Specific contents of the compound in each of the above layers are shown below.

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After cutting the samples prepared as described above, a sensitometer (manufactured by Fuji Photo Film Co., Ltd.) FW type was added to each sample.
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. Thereafter, a sample subjected to white light exposure was prepared and subjected to the same processing steps.

Processing process Temperature Time Replenishment amount * Tank capacity Color development 40 ° C. 20 seconds 2 liters Bleaching and 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 ° C. 5 seconds - 1 liter rinse 40 ° C. 5 seconds - 1 liter rinse 40 ° C. 5 seconds 60 ml 1 liter drying 60-80 ° C. 15 seconds * replenishment rate is per photosensitive material 1 m ² (5 tanks countercurrent to rinse → The rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for use. The composition of each processing solution is as follows. The color developer was composed of two replenishers and replenished so that they were not 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 monohydrate Sulfinic acid salt (S-5) 0.4 g Sodium sulfite 0.06 g 1,2-dihydroxybenzene-4,6-disulfonic acid 2 g 0.5 g Thorium Water is added, and 100 ml pH (25 ° C.) 3.5 [ Second replenisher] Triethanolamine disodium-N, N-bis (sulfonatoethyl) hydride 4.6 g Roxylamine sodium triisopropylnaphthalene (β) 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 and 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 to 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) Ammonium iron (III) ethylenediaminetetraacetate 77 g Disodium ethylenediaminetetraacetate 5 g Ammonium chloride 42 g Acetic acid (50%) 116 ml Add water 1000 ml pH ( (25 ° C) (adjusted with acetic acid and aqueous ammonia)

Rinse solution Deionized water (calcium, magnesium 3 ppm each)
[Evaluation of Desilvering Performance] The amount of residual silver was measured using a fluorescent X-ray analyzer for the white exposed film of the sample after the treatment. [Evaluation of image stain over time] After the treatment, the sample (imagewise exposed film) was stored for 7 days in a thermo-hygrostat adjusted 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] The maximum density of cyan (D) of the processed sample (film subjected to imagewise exposure) was measured using a photographic densitometer FSD103 manufactured by Fuji Photo Film Co., Ltd.
_max ) was measured. The stain level of the sample (Fr) after the treatment was visually examined. The evaluation was determined based on the following criteria. Almost none: ，, partially observed: Δ, present on entire image: × [Evaluation of liquid stability] The rinse solution left after standing after running was visually examined for the degree of turbidity. The evaluation was determined 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-fix solution is
Continuous processing was performed until the tank capacity was doubled. Then 7
The performance and the state of the rinsing liquid of the sample that had been left untreated for a day and then reprocessed were observed. The rinsing liquid is a submerged blade system (II) in which a multistage countercurrent washing bath having blades in a bathtub shown in FIG. 3 is used, and a conventional roller shown in FIG. Transport method
(I) was carried out. FIG. 6 is a configuration diagram showing a conventional transport system.
Is transported alternately in water and in the air. Further, processing was performed using a conventional ATS in place of the fixing agent of the present invention, and a comparative example was obtained. Table 6 shows the results.

[0110]

[Table 6]

As can be seen from Table 6, according to the present invention, even after a short bleach-fixing and washing with water, the desilvering property, Fr and stain after aging are good, and the stability of the rinsing liquid is good. It can be seen that an excellent result is obtained. Further, in the present invention, there is little contamination such as deposits on the blade portion, and the blade need not be cleaned. On the other hand, in the method using the conventional ATS, suspended matter adhered to the blade portion, and the cleaning frequency was high.

Example 2 Example 1 was repeated except that the color developing step and the washing method were changed as described below using the photosensitive material used in Example 1.
A similar test was performed. Processing process temperature Time replenishment amount * Tank capacity Color development 40 ° C 15 seconds 35 ml 2 liter Bleach-fix 40 ° C 15 seconds 35 ml 2 liter Rinse 40 ° C 5 seconds-1 liter Rinse 40 ° C 5 seconds-1 liter Rinse 40 ° C 5 s - (. was 3 tank countercurrent system to rinse →) 1 liters drying 60-80 ° C. 15 seconds 120 ml * replenishment rate is per photosensitive material 1 m ²

[0113] 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 and used. The color developer was the following developer, and the same bleach-fixer as in Example 1 was used. The processing method is the same as the conventional roller conveyance method (I) implemented in Example 1.
In addition to the submerged blade system (II), a system using a submerged blade having the configuration shown in FIG. The conveying speed of the photosensitive material is 1.4 cm / sec, the diameter of the processing roller is 3 cm, the rotation speed is 750 rpm, and the surface shape of the processing roller is a spiral having a pitch of 2 mm inclined at 10 ° to the conveying direction of the photosensitive material.

Color developer tank solution 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 bicarbonate 5.3 g --- Fluorescent 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- 13.1 g 33.0 g (4-hydroxybutyl) aniline · 2p-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. Table 7 shows the results of Example 2.

[0116]

[Table 7]

The results shown in Table 7 indicate that the treatment (I
(I) and (III) have better desilvering properties than the conventional treatment (I),
It can be seen that there is little Fr stain and stain with time, and the stability of the rinsing liquid is good. It was also found that the stain with time can be further reduced by combining the submerged blade and the processing roller in the processing (III).

Example 3 The same processing as in Example 1 was performed except that the light-sensitive material 2 described below was used in place of the light-sensitive material used in Example 1 and the exposure method was described below. The rinse is shown in FIG.
The submerged blade method shown in Fig. 1 was used. (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'-dimethylimidazolidin-2-thione (2% aqueous solution) was added. An aqueous solution containing 0.2 mol of silver nitrate in the aqueous solution;
0.2 mol of sodium chloride and 15μ of rhodium trichloride
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 completion of the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution, an aqueous solution further containing 0.020 mol of silver nitrate and 0.01 ml of potassium bromide were added.
An aqueous solution containing 5 mol, 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridate (IV) was added and mixed at 40 ° C. with vigorous stirring. Thereafter, a copolymer of isobutene maleic acid 1-sodium salt was added, and the mixture was washed by settling and desalting. Further, 90.0 g of lime-processed gelatin was added, and the pH of the emulsion, pAg
Was adjusted to 6.2 and 6.5, respectively. Further, a sulfur sensitizer (triethylthiourea) 1 × 10 ⁻⁵ mol / mol Ag
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 an electron micrograph. Each of these silver halide grains is cubic, and the grain size is 0.52 μm.
08. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size. Next, the halogen composition of the emulsion grains was determined by measuring X-ray diffraction from silver halide crystals. The diffraction angle from the (200) plane was measured in detail using the monochromatic Cukα ray as a radiation source. Diffraction lines from crystals having a uniform halogen composition give a single peak, whereas diffraction lines from crystals having localized phases with different compositions give a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the measured diffraction angle of the peak, the halogen composition of the silver halide constituting the crystal can be determined. The measurement results of this silver chlorobromide emulsion (a) show that the center is at 70% of silver chloride (30% of silver bromide) and 60% of silver chloride (40% of silver bromide) in addition to the main peak of 100% of silver chloride. , A broad diffraction pattern with a skirt extending to the vicinity of was observed.

(Preparation of Photosensitive Material 2) After a 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. Thus, a multilayer color photographic paper having the following layer structure was produced.
The coating solution was prepared as follows. Preparation of First Layer Coating Solution 19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-)
7) 27.2 cc of ethyl acetate and solvent (S
olv-3) and (Solv-7) in 4.1 each.
g of the resulting solution, and the resulting solution is dissolved in a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed to 85 cc to prepare an emulsified dispersion. On the other hand, a silver chlorobromide emulsion (a) was coated with a red-sensitive sensitizing dye (Dy) shown below.
An emulsion to which e-1) was added was prepared. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s
-Triazine sodium salt was used. In addition, Cp is added to each layer.
The total amount of each of d-10 and Cpd-11 was 25.0 mg.
/ M ² and 50.0 mg / m ² . The following were used as spectral sensitizing dyes for each layer.

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[0122]

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Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the yellow, magenta and cyan coloring emulsion layers at 8.0 × 10 ^-4 per mol of silver halide. Mole was added. The following dyes were added to the emulsion layer to prevent irradiation.

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[0126]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (red-sensitive yellow coloring layer) Silver chlorobromide emulsion (a) 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 mixture prevention layer) Gelatin 0.64 Color mixture prevention agent (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third layer (infrared-sensitive magenta color-forming 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 (ultraviolet light) Absorbing 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 coloring 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 ray absorbing layer) Gelatin 0.48 Ultraviolet ray absorbent (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

The specific contents of the compounds in each of the above layers are the same as those described in Example 1. Table 8 shows the fixing agents in the bleach-fix solution. 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. Each of the laser beams is a device capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to a scanning direction by a rotating polyhedron. The relationship between the density (D) of the photosensitive material and the light amount (E) is obtained by changing the light amount using this apparatus.
I asked. The light amount of the semiconductor laser was controlled by combining a pulse width modulation method for modulating the light amount by changing the energizing time to the semiconductor laser and an intensity modulation method for modulating the light amount by changing the energizing amount. This scanning exposure is 40
At 0 dpi, the average exposure time per pixel at this time is about 10 ^-7 seconds. Table 8 shows the results of Example 3.

[0132]

[Table 8]

From the results shown in Table 8, the submerged blade system (I
In (I), when the fixing agent of the present invention was used, the desilvering property was extremely good as compared with the case where the conventional ATS was used.
There was little r-stain and aging stain, and the stability of the rinsing solution was good, and all showed better results than before.

[Brief description of the drawings]

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

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

FIG. 3 is a configuration diagram of a modified example 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 means.

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 Bleaching and fixing tank 16 Rinse tank 17 Drain section 18 Drying section 20 Photosensitive material 24 Conveying roller pair 26 Reverse osmosis membrane device 28 Pump 30 Fan 32 Slit 54 Processing roller 56 Shutter means 58 Blade 60 Tank wall 62 Slit

Claims (4)

(57) [Claims] 1. A method for exposing and developing a photographic material having at least one layer comprising a photosensitive silver halide emulsion on a support, comprising: after development, a nitrogen-containing heterocycle having a sulfide group as a fixing agent after development. After treating with a bath having a fixing ability containing at least one compound of the compound, mesoionic compound or thioether compound, washing and / or stabilizing treatment are carried out in multi-stage countercurrent.
When performing in a bath, make sure that the photosensitive material does not come into contact with air.
A photographic light-sensitive material, which is moved in water to be washed and / or stabilized. 2. The method according to claim 1, wherein the silver halide emulsion contains 90% silver chloride.
2. The composition according to claim 1, which contains at least mol% of particles.
3. The method for processing a photographic light-sensitive material according to item 1. 3. The photosensitive material is provided in contact with the peripheral surface of a processing roller in the processing liquid in 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 transport speed. 3. The method according to claim 1, wherein the processing is performed by rotating the processing roller at 75 rpm or more. 4. The method for processing a photographic light-sensitive material according to claim 1, wherein the opening ratio of the bath to be washed and / or stabilized is 0.001 or less.