JPH04365036A - Processing for silver halogenide color photosensitive material - Google Patents

Abstract

PURPOSE:To quickly provide an image having excellent desilvering property, little image stain and high maximum density by processing a photosensitive material with a solution containing a specific compound. CONSTITUTION:A silver halogenide color photosensitive material containing silver chloride 90mol.% or above is processed by bleach fixing within 25 sec with a bleach-fixing solution containing at least a compound 0.1 mole/l among compounds expressed by formulas I, II, III and having pH 2-5, where Q201 indicates the atom group necessary to form a five or six-membered heterocycle, R201 indicates carboxylic acid or its salt, (q) indicates an integer 1-3, M201 indicates cation group, Q301 indicates a five or six-membered mesoion ring, X301<-> indicates -O<->, -N<->R301, R301 indicates alkyl group, L401 and L403 indicate alkyl group and allyl group respectively, L402 indicates alkylene group and allylene group, A401 and A401 indicate -S-, -O respectively, and (r) indicates an integer 1-10.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically to a method for processing a silver halide color photographic light-sensitive material that has excellent desilvering properties, liquid stability, and little image stain. This relates to a processing method.

0002

2. Description of the Related Art Processing of silver halide color photographic materials generally consists of a color development process and a silver removal process. In the silver removal process, the developed silver produced during the color development process is oxidized (bleached) to silver salt by a bleaching agent that has an oxidizing effect, and is further removed from the photosensitive layer by a fixing agent that forms soluble silver together with unused silver halide. be done. (Fixing) As the bleaching agent, ferric (III) ion complex salts (for example, aminopolycarboxylic acid-iron (III) complex salts) are mainly used.
Thiosulfates are commonly used as fixing agents. Bleaching and fixing may be carried out as independent bleaching and fixing steps, or may be carried out simultaneously as a bleach-fixing step. Details of these processing steps can be found in James' The Theory of Photography.
James, “The Process” 4th edition (James, “The Process” 4th edition)
ory of Photographic Pr
4'th edition) (1977
year). The above processing steps are generally performed using an automatic processor. Particularly in recent years, small automatic processing machines called minilabs have been installed in stores, and rapid processing services have become widespread for customers. A bleaching agent and a fixing agent are used in the same bath as a bleach-fixing bath in color paper processing due to miniaturization of developing machines and speedy processing. In recent years, there has been a strong demand for speeding up processing steps and ease of maintenance, and it is also desired that bleach-fixing steps be greatly speeded up and liquid stability improved. Furthermore, as processing has come to be carried out in various locations, the problem of processing waste liquid has become more serious.

Ethylenediaminetetraacetic acid ferric complex salts have traditionally been used in bleaching processes. Other bleaching agents that have strong oxidizing power and achieve rapid bleaching include red blood salt;
Although iron chloride, etc. are known, among red blood salts,
Due to environmental protection issues, iron chloride cannot be widely used due to inconvenience in handling such as metal corrosion. Recently, 1,3-diaminopropanetetraacetic acid ferric complex salt has been disclosed as a versatile bleaching agent having rapid bleaching properties. However, when this bleach was used, it was not sufficient because bleaching often caused bleaching fog.

On the other hand, thiosulfate used as a fixing agent undergoes oxidative deterioration, sulfurizes, and forms a precipitate, so in most cases sulfite is added as a preservative to prevent oxidation. However, as low replenishment progresses, further improvements in liquid stability are desired, but adding an increased amount of sulfite cannot solve the problem of solubility and the formation of mirabilite precipitates when sulfite is oxidized. It's coming. Moreover, the lower the pH of the liquid, the more these problems become serious. Also, from the viewpoint of speeding up the process, a compound with better fixing properties than thiosulfuric acid is desired. On the other hand, the use of mesoionic compounds as a fixing agent in place of thiosulfate has been described in US Pat. do not have. In addition, 1,2 in JP-A No. 2-44355
, 4-triazolium-3-thiolate compound is added to a fixing bath as a fixing agent.
-201659 discloses adding a mesoionic compound as a bleaching accelerator to a bleaching bath or a bleach-fixing bath; There is no description at all, and there is also no description of the intended effects of the present invention. In addition, when used as an accelerator, it is often effective with a small amount of use, and also has a role such as removing substances adsorbed to silver halide (or silver). Since the amount used and the role (function) are very different from those when used as a fixing agent, the present invention cannot be easily inferred. In addition, as a mesoionic compound, US Patent No. 4,000
No. 3,910, No. 4,675,276, No. 4,624
, No. 913, No. 4,631,253, JP-A-62-2
No. 17,237, No. 64-3,641, No. 60-14
No. 4,737, No. 62-253,161, No. 62-2
No. 87,239, No. 61-176,920, No. 62-
No. 96,943 and Japanese Unexamined Patent Publication No. 1-154,056 disclose, but all of them are additives to photographic light-sensitive materials or to developer solutions, and they do not have the effect of the present invention. It doesn't say anything. Thiosulfate is currently the most commonly used fixing agent because there is no substitute for it in terms of cost and fixing ability. Generally, a bleach and a fixing agent are used in the same bath as a bleach-fixing bath in color paper processing from the viewpoint of speed. High oxidizing power (high redox potential) 1,3 to increase bleaching power
Oxidizing agents such as diaminopropane tetraacetic acid ferric complex salts have come into use in bleach-fix baths. However, even in bleach-fixing baths, the aforementioned bleach fog may occur,
Since the thiosulfate is bleached and fixed, the oxidative deterioration of the thiosulfate is further increased, so it cannot be said to be suitable for practical use. This problem has become a fatal flaw as replenishment levels have progressed in recent years. In addition, when rapid bleach-fixing is performed after rapid color development, developing agents and sensitizing dyes and dyes used in light-sensitive materials, which were previously removed in the bleach-fixing process, are not sufficiently removed. Stain is starting to appear on the image. Therefore, there has been a strong desire for the development of fixing agents and bleaching agents that solve the above-mentioned problems, as well as processing compositions and processing methods using them.

[0005]

[Problems to be Solved by the Invention] Therefore, the present inventors investigated various fixing agents with excellent oxidation stability to replace thiosulfate, and found that the compound of the present invention has fixing ability and is stable against oxidation. It has been found that no precipitate is formed even when a low replenishment amount is used, and that the bleach fog is smaller than in the case of thiosulfate, and good results are obtained especially when the bleach-fix is used in combination with a high-potential oxidizing agent. In particular, the fixing ability of silver halide salts is better as the pH of the bleach-fixing bath is lower.
Rapid fixing became possible at H5 or lower. It was surprising that the fixing ability was significantly improved at such a low pH. This may be because the carboxyl groups of gelatin are not dissociated at low pH, and therefore the interaction with the produced silver salt is reduced. However, this is still in the realm of speculation. Further, if the treatment is carried out at a pH of 2 or less for a long period of time, the maximum concentration of the cyan dye decreases, which is not preferable. Further, it was not preferable to carry out the treatment for more than 25 seconds in terms of a decrease in the maximum density. In other words, by processing within 25 seconds, it has become possible to maintain both fixing ability and image density. Furthermore, as mentioned above, the short processing time of bleach-fixing is insufficient to remove the color developing agent, sensitizing dye, dye, etc. brought in from the color developing bath, and the shorter the total processing step, the longer the bleach-fixing processing time will be. has become difficult to shorten. Particularly, the removal of the developing agent is a serious problem, and when the bleach-fixing time and the water washing or stabilizing treatment time are shortened, stains are clearly formed on the image and the harmful effects thereof are observed. Regarding the removal of developing agents, structural differences were also observed, and in particular, it was found that the developing agents used for rapid development in the present invention are difficult to remove with conventional bleach-fix solutions. However, when treated with the bleach-fix bath of the present invention, it has been unexpectedly found that even the rapid developing agent described in the present invention can be removed very quickly. Therefore, the first aspect of the present invention
The purpose of this is to provide a processing method with excellent desilvering properties. A second object of the present invention is to provide a processing method that includes a bleach-fix bath that causes less bleach fog and has excellent liquid stability. A third object of the present invention is to provide a processing method that enables rapid desilvering processing and shortens the total processing time. A fourth object of the present invention is to provide a low replenishment, rapid processing method with less image stain.

[0006]

[Means for Solving the Problems] The above object has been achieved by the following processing method. (1) In a processing method in which a silver halide color photographic light-sensitive material having at least one light-sensitive halide emulsion layer on a support is subjected to color development and bleach-fixing after exposure, a halogen containing 90 mol% or more of silver chloride is used. A bleach-fixing solution containing at least one compound of the following general formula (A), (B), or (C) at least 0.1 mol/l and having a pH of 2 or more and 5 or less for silveride color photographic light-sensitive materials. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises performing a bleach-fixing process within 25 seconds using a method for processing a silver halide color photographic material. General formula (A)

[0007]

embedded image In the formula, Q201 represents an atomic group necessary to form a 5- or 6-membered heterocycle. Further, this heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring. R201 is a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or a monocyclic group substituted with at least one of an amino group or an ammonium salt. Represents a bond. q represents an integer of 1 to 3, and M201 represents a cationic group. General formula (B)

[0008]

embedded image In the formula, Q301 represents a 5- or 6-membered mesoion ring composed of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or selenium atom, and X301- is -O-, -S-
Or it represents -N-R301. R301 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. General formula (C)

[0009]L401-(A401-L402)r-A
402-L403 In the formula, L401 and L403 may be the same or different and each represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a heterocyclic group, and L402 is an alkylene group, an arylene group, an aralkylene group, or a heterocyclic linkage. Represents a group or a linking group combining them. A401 and A402 may be the same or different and may be -S-, -O-, -NR420-, -, respectively.
Represents CO-, -CS-, -SO2- or any combination thereof. r represents an integer from 1 to 10. However, at least one of L401 and L403 is -SO3
M401, -PO3M402M403, -NR401(
R402), -N+R403 (R404) (R405)
・X401-, -SO2NR 406 (R407), -NR408SO2R409, -
CONR410 (R411), -NR412COR41
3, -SO2R414, -PO(-NR415(R41
6)) 2, -NR417CONR 418 (R419), -COOM404 or a heterocyclic group. M401, M402,
M403 and M404 may be the same or different and each represents a hydrogen atom or a counter cation. M401~M40
2 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an alkenyl group, and X401- represents a counter anion. However, at least one of A401 and A402 represents -S-.

(2) The bleach-fix solution has the following general formula (I), (
The silver halide color photographic light-sensitive material according to (1), which contains at least one metal chelate compound consisting of a compound represented by II), (III), (IV) or (V). Processing method. General formula (I)

[0011]

embedded image In the formula, X is -CO-N(OH)-Ra, -N(OH)-
CO-Rb (here, 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), -SO2NRc (Rd
) or -N(Re)SO2Rf (where Rc, Rd and Re represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Rf represents an aliphatic group, an aromatic group or a heterocyclic group). ) represents. L1 represents a divalent linking group containing an aliphatic group, an aromatic group, a heterocyclic group, or a group consisting of a combination thereof. R11 and R12 may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. General formula (II)

0012

embedded image In the formula, R21 has the same meaning as R11 in general formula (I). R
2a and R2b may be the same or different, and each -
Y1-C(=X1)-N(Rh)-Rg or -Y2-
N(Ri)-C(=X2)-Rj (where Y1 and Y
2 has the same meaning as L1 in general formula (I). Rg, Rh and Ri have the same meanings as Ra in general formula (I). Rj is an aliphatic group, an aromatic group, a heterocyclic group, -NRk (R1) (where Rk and R1 have the same meaning as Ra in general formula (I)) or -ORm (where Rm is an aliphatic group) , represents an aromatic group or a heterocyclic group). X1 and X2 represent an oxygen atom or a sulfur atom. )represent. General formula (III)

[0013]

embedded image In the formula, R31, R32 and R33 are R in general formula (I)
It is synonymous with 11. R3a has the same meaning as R2a in general formula (II). W represents a divalent linking group. General formula (IV)

[0014]

embedded image In the formula, R41 and R42 have the same meaning as R11 in general formula (I). L2 represents a divalent linking group. Z represents a heterocyclic group. n represents 0 or 1. General formula (V)

[0015]

embedded image In the formula, L3 represents a divalent linking group containing an aliphatic group, an aromatic group, a heterocyclic group, or a combination thereof. A represents a carboxyl group, a phosphono group, a sulfo group or a hydroxy group. R51, R52, R53, R54, R
55, R56 and R57 may be the same or different and each represents a hydrogen atom, an aliphatic group or a heterocyclic group. R58
and R59 may be the same or different and each hydrogen atom,
Represents an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfinyl group. Further, R58 and R59 may be connected to form a ring. t and u represent 0 or 1.

(3) The color developing solution has the following general formula (Dev)
The method for processing a silver halide color photographic light-sensitive material according to (1) or (2), characterized in that it contains a p-phenylenediamine derivative represented by the following. General formula (Dev)

embedded image In the formula, R1 and R3 are alkyl groups having 1 to 4 carbon atoms,
R2 is a 3-4 linear or branched alkylene group.

(4) The silver halide photograph described in (1) or (2), characterized in that the processing time of the photosensitive material is within 120 seconds from the beginning of the developing process to the end of the drying process. How materials are processed.

Although the present invention enables rapid processing, it also enables processing in a system where the influence of air outside the processing bath is large. It is possible to carry out satisfactorily processing even with a large processing device. Additionally, low replenishment amounts can be processed for similar reasons. The open area ratio is a value obtained by dividing the surface area of a processing tank by the volume of the processing tank, and is often used as an index of the oxidizability of the processing liquid in the processing tank. The present invention is a processing method aimed at quick and simple processing, and the alkali consumption is 3.0 mmo.
A photosensitive material having a density of 1/m2 or less can be preferably used. Alkali consumption is defined as the amount of alkali required to raise the pH from 6 to 10 by pulverizing a photosensitive material using a support, as described in JP-A-3-109549. The present invention will be explained in detail below. The bleach-fixing composition in the present invention is generally a bleach-fixing solution, but also includes its replenisher, supply kit (liquid or sticky agent), and the like. The replenishing fluid may be divided into two or more types and replenished.

The compound represented by the general formula (I) will be explained in detail below. In general formula (I), X is -CO
-N(OH)-Ra, -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. ), -SO2NRc(Rd) or -NRe-
SO2Rr (where Rc, Rd and Re are hydrogen atoms,
Represents an aliphatic group, an aromatic group, or a heterocyclic group. Rf represents an aliphatic group, an aromatic group or a heterocyclic group. ) represents. L1 represents a divalent linking group containing an aliphatic group, an aromatic group, a heterocyclic group, or a group consisting of a combination thereof. R1
1 and R12 each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

The aliphatic group represented by Ra is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, preferably having 1 to 10 carbon atoms. More preferred aliphatic groups are alkyl groups, particularly preferred are alkyl groups having 1 to 4 carbon atoms. The aromatic group represented by Ra is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group, with a phenyl group being more preferred. The heterocyclic group represented by Ra is N, O or S
A 3- to 10-membered saturated or unsaturated heterocycle containing at least one atom, which may be a single ring or may form a fused ring with another aromatic ring or heterocycle. good. The heterocycle is preferably a 5- to 6-membered aromatic heterocycle, such as thiophene,
Furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, Examples include phenazine, tetrazole, thiazole, and oxazole. More preferred aromatic heterocyclic groups include pyrrole, imidazole, pyrazole, pyridine,
These include pyrazine, pyrimidine, triazole, thiadiazole, oxadiazole, quinoxaline, tetrazole, thiazole, and oxazole, with pyrrole, imidazole, pyridine, triazole, thiadiazole, oxadiazole, quinoxaline, tetrazole, thiazole, and oxazole being particularly preferred.

Ra may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an amino group, an acylamino group, a sulfonylamino group, and a ureido group. , urethane group, aryloxy group, sulfamoyl group,
Carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, nitro group, hydroxamic acid group, heterocyclic group, etc. The aliphatic group, aromatic group, and heterocyclic group represented by Rb, Rc, Rd, Re, and Rf are Ra
It has the same meaning as the aliphatic group, aromatic group, and heterocyclic group represented by.

[0022] Furthermore, Rc and Rd, and Re and Rf may be connected to each other to form a ring. Examples of the ring formed by linking include a morpholine ring, a piperidine ring, a pyrrolidine ring, and a pyrazine ring. L1 is an aliphatic group,
Represents a divalent linking group containing an aromatic group, a heterocyclic group, or a combination thereof. Divalent linking groups include alkylene groups having 1 to 10 carbon atoms, and 6 to 1 carbon atoms.
0 arylene group, an aralkylene group having 7 to 10 carbon atoms, or -O-, -S-, -CO-, -NR0-(R0
is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or a hydroxy group), and a group consisting of a combination of -SO2- and an alkylene group or an arylene group is preferable. Furthermore, a combination of these may be used if possible. Further, these divalent linking groups may have a substituent, and for example, those listed as the substituent for Ra can be applied. L1
Preferred specific examples include the following, with methylene and ethylene groups being particularly preferred.

[0023]

[Chemical formula 17]

R11 and R12 may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. The aliphatic group represented by R11 and R12 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, preferably having 1 to 10 carbon atoms. More preferred aliphatic groups are alkyl groups, particularly preferred are alkyl groups having 1 to 4 carbon atoms. The aromatic group represented by R11 and R12 is a monocyclic or bicyclic aryl group, such as a phenyl group or a naphthyl group. A phenyl group is more preferred. R11
and the heterocyclic group represented by R12 is R of general formula (I).
It has the same meaning as the heterocyclic group represented by a. Further, R11 and R12 may have a substituent, and as the substituent, for example, those listed as the substituent for Ra can be applied. Furthermore, at least one of R11 and R12 is -
OH, -COOM1, -PO3M2M3 or -SO3
M4 (Here, M1, M2, M3, and M4 may be the same or different and each represents a hydrogen atom or a cation. Examples of the cation include alkali metals (lithium, sodium, potassium, etc.), ammonium, pyridinium, etc.) An alkyl group, aryl group or heterocyclic group having -COO as a substituent is preferable.
More preferably, it is an alkyl group, an aryl group, or a heterocyclic group having M1 as a substituent. Furthermore, R11, R12, X, and L1 may be connected to form a ring if possible. Among the compounds represented by general formula (I), preferably the following general formulas (VI) and (VII)
, (VIII) or (IX).

[0025]

[Chemical formula 18]

In the formula, R11, Ra, and L1 represent the general formula (I)
are synonymous with each of L61, L71, L72, L
73 and L81 have the same meaning as L1 in general formula (I). R71 has the same meaning as Ra in general formula (I). M61, M71, M72, and M81 represent a hydrogen atom or a cation (alkali metal, ammonium, pyridinium, etc.). X81 and X91 are -SO2NRc(Rd
) or -NRe-SO2Rf (Rc, Rd, Re, R
f has the same meaning as each of general formula (I). ) represents. R91, R92 and R93 are R in general formula (I)
11, R91, R92, R93 and X9
1-L1 may be the same or different from each other. Furthermore, at least one of R91, R92, and R93 is Lx1-COOMx1 or Lx2-X92 (Lx1,
Lx2 has the same meaning as L1 in general formula (I). Mx
1 represents a hydrogen atom or a cation (alkali metal, ammonium, pyridinium, etc.). X92 is the general formula (I
It has the same meaning as X91 in X). ) is preferable.

W represents a divalent linking group. The divalent linking group is preferably an alkylene group having 2 to 8 carbon atoms,
Arylene group having 6 to 10 carbon atoms, 7 to 1 carbon atoms
0 aralkylene group, cyclohexane group, heterocyclic group,
-(W1-O-)p-W2-, -(W1-S-)p-W
2- (W1, W2 represent an alkylene group, arylene group, aralkylene group or heterocyclic group. p represents 1, 2 or 3), -W1-NB-W2- (B is hydrogen, hydrocarbon, - La-COOMa1, -La-PO3Ma2M
a3, -La-OH, -La-SO3Ma4 (La represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 10 carbon atoms, an aralkylene group having 7 to 10 carbon atoms, or a heterocyclic group. Ma1, Ma2 , Ma3, Ma
4 represents a hydrogen atom or a cation (alkali metal, ammonium, pyridinium, etc.). ), and combinations thereof may also be used. These divalent linking groups may have a substituent, and examples of the substituent include Ra
Those listed as substituents can be applied. Specific examples of W include the following.

[0028]

[Chemical formula 19]

The compound represented by the general formula (II) will be explained in detail below. In general formula (II), R21
has the same meaning as R11 in general formula (I). R2a and R
2b may be the same or different, and each -Y1-C (=
X1)-NRh-Rg or -Y2-NRi-C (=X
2) -Rj (where Y1 and Y2 are L in general formula (I)
It is synonymous with 1. Rg, Rh and Ri are general formula (I)
It is synonymous with Ra. Rj is an aliphatic group, an aromatic group, a heterocyclic group, -NRk(RL) (here, Rk and RL have the same meaning as Ra in general formula (I)), or -ORm (here, Rm is an aliphatic group) , represents an aromatic group or a heterocyclic group). X1 and X2 each independently represent an oxygen atom or a sulfur atom. ) represents. The aliphatic group, aromatic group, and heterocyclic group represented by Rm are synonymous with the aliphatic group, aromatic group, and heterocyclic group represented by Ra in general formula (I). Furthermore, Rg and Rh, Ri and Rj, and Rk and RL may be connected to each other to form a ring. Examples of the ring formed by linking include a morpholine ring, a piperidine ring, a pyrrolidine ring, and a pyrazine ring. Among the compounds represented by general formula (II), compounds represented by the following general formula (X) are preferred.

[0030]

[C20]

In the formula, Ra and LL have the same meanings as in general formula (I). L101 and L102 have the same meaning as L1 in general formula (I). R101, R102 and R103
has the same meaning as Ra in general formula (I). M101 has the same meaning as M61 in general formula (VI). The compound represented by general formula (III) will be explained in detail below. General formula (
In III), R31, R32 and R33 have the same meaning as R11 in general formula (I). R3a is general formula (II)
It has the same meaning as R2a. W has the same meaning as in general formula (VII). Among the compounds represented by the general formula (III), preferably the compound represented by the following general formula (XI).

[0032]

[C21]

In the formula, Ra and L1 have the same meanings as in general formula (I). L111, L112 and L113 have the same meaning as L1 in general formula (I). R111, R112
and R113 has the same meaning as Ra in general formula (I). M
111 and M112 have the same meaning as M61 in general formula (VI). W has the same meaning as in general formula (VII).

The compound represented by the general formula (IV) will be explained in detail below. In the formula, R41 and R42 have the same meaning as R11 in general formula (I). Z represents a heterocyclic group, and has the same meaning as the heterocyclic group represented by Ra in general formula (I). n represents 0 or 1. L2 represents a divalent linking group. The divalent linking group is a straight chain, branched or cyclic alkylene group, alkenylene group or alkynylene group (
Preferably it has 1 to 10 carbon atoms, more preferably an alkylene group, and particularly preferably an alkylene group having 1 to 4 carbon atoms. ), arylene group (preferably having 6 to 10 carbon atoms, such as phenylene group and naphthalene group), aralkylene group (preferably having 7 to 10 carbon atoms), -CO-, -SO2- or -O- ,-S
-, -CO-, -NRoo- (where Roo is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or a hydroxy group), a combination of -SO2- and an alkylene group, an arylene group, or a heterocyclic group. A group consisting of is preferred. Furthermore, if possible, a combination of these groups may be used. Further, these divalent linking groups may have a substituent, and as the substituent, for example, those listed as the substituent for Ra can be applied. Preferred specific examples of L2 include the following.

[0035]

[C22]

Furthermore, R41, R42, Z, and L2 may be connected to form a ring if possible. General formula (IV)
Among the compounds represented by the following general formula (XI
I) and or (XIII).

[0037]

[C23]

In the formula, Z and L2 have the same meanings as in general formula (IV). W has the same meaning as that in general formula (VII). R121 and R122 have the same meaning as R11 in general formula (I), and R121, R122 and Z-L2 may be the same or different from each other. R121 and R1
22 is preferably -Lb-OH, -Lb-COOM
b1, -Lb-PO3Mb2Mbs, -Lb-SO3M
b4 (Mb1, Mb2, Mb3, Mb4 each represent a hydrogen atom or a cation. Examples of the cation include alkali metals (lithium, sodium, potassium, etc.), ammonium, pyridinium, etc. Lb is generally Synonymous with L1) or -LB
-Za (LB has the same meaning as L2 in general formula (IV), and Za has the same meaning as Z in general formula (IV).)
and more preferably -LB-COOMb1 or -
It is LB-Za.

R131, R132 and R133 have the same meaning as R11 in general formula (I), and R131, R133
32, R133, and Z-L2 may be the same or different from each other, and at least one of R131, R132, and R133 is Zb-Lc (Lc is synonymous with L2 in general formula (IV), and Zb general formula (IV ) is preferably the same as Z in ).

The compound represented by the general formula (V) will be explained in detail below. L3 is L1 in general formula (I)
is synonymous with A represents a carboxyl group, a phosphono group, a sulfo group, or a hydroxy group, preferably a carboxyl group or a hydroxy group, and more preferably a carboxyl group. R51, R52, R53, R54, R55, R5
The groups, aromatic groups, and heterocyclic groups represented by 6, R57, R58, and R59 have the same meanings as those represented by Ra in general formula (I).

[0041] An acyl group represented by R58 and R59,
The sulfamoyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group and sulfinyl group preferably have 10 or less carbon atoms. Hydrogen atoms are preferred as R51, R52, R53, and R54. Furthermore, R58 and R59 are preferably in the cis position. Furthermore, R58 and R59 may be connected to form a ring. t and u represent 0 or 1, preferably at least one of t and u is 1, more preferably both t and u are 1. Among the compounds represented by the general formula (V), a compound represented by the following general formula (XIV) is preferred.

[0042]

[C24]

In general formula (XIV), A, L3, R
51, R52, R53, R54, R55, R56, R5
7, t and u have the same meanings as in general formula (V). In general formula (XIV), Q represents a 5- or 6-membered nonmetallic atom group. 5 or 6 members formed by Q
Examples of member rings include aromatic rings (e.g. benzene, naphthalene,
phenanthrene, anthracene), heterocycles (e.g. pyridine, pyrazine, pyrimidine, pyridazinethiophene, furan, pyran, pyrrole, imidazole, pyrazole, isothiazole, isoxazole, thianthrene, isobenzofuran, chromene, xanthene, phenoxathin, indolizine, isoindole) , indole,
indazole, quinolidine, isoquinoline, quinoline,
Phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine, pteridine, phenanthroline, phenazine, phenothiazine, phenoxazine, chroman, pyrroline, pyrazoline, indoline,
isoindoline), cyclic alkenes (e.g. cyclopentene, cyclohexene), and the like. Further, these rings may be further condensed with other rings. The ring formed by Q is preferably benzene, naphthalene, pyridine,
These include pyrazine, pyrimidine, quinoline, and quinoxaline, and more preferably benzene.

The ring formed by Q may have a substituent, and examples of the substituent include those listed as the substituent for Ra in formula (I). Among the compounds represented by the general formula (V), the following general formula (XV) is more preferable.
This is a compound represented by

[0045]

[C25]

(In the formula, Q, A, L3, R51, R52,
R53, R54, R56, R57, t, u are represented by the general formula (X
IV). L151 has the general formula (V
), and A1 has the same meaning as A in general formula (V). ) Among the compounds represented by the general formula (V), the compounds represented by the following general formula (XVI) are particularly preferred.

[0047]

[C26]

(In the formula, Q, A, L3, R51, R52,
R53, R54, t, and u have the same meanings as in general formula (XIV). L161, L162 and L163 each have the same meaning as L3 in general formula (V), and A2, A3 and A4 each have the same meaning as A in general formula (V). )
Specific examples and synthetic methods of compounds represented by general formulas (I), (II), (III), (IV) and/or (V) are disclosed in Japanese Patent Application Nos. 2-127,479 and 2-175,02.
No. 6, No. 2-196,972, No. 2-201,846
No. 2-258,539. Representative examples of compounds represented by general formulas (I), (II), (III), (IV) and/or (V) are shown below, but are not limited thereto.

[0049]

[C27]

[0050]

[C28]

[0051]

[C29]

[0052]

[C30]

[0053]

[Chemical formula 31]

[0054]

[C32]

Examples of the central metal used in the metal chelate compound of the present invention include Fe(III) and Mn(III).
), Co(III), Rh(II), Rh(III),
Examples include Au(III), Au(II), Ce(IV), and the like. The metal chelate compound of the present invention may be an isolated metal chelate compound. Of course, in the present invention, general formulas (I), (II), (III)
), (IV) and/or (V) and metal salts, such as ferric sulfate complex salts, ferric chloride salts, ferric nitrate salts, ferric ammonium sulfate, ferric phosphate salts etc. may be used by reacting them in a solution. The compound represented by the general formula (I), (II), (III), (IV) and/or (V) is used in a molar ratio of 1.0 or more to the metal ion. This ratio is preferably larger when the stability of the metal chelate compound is low, and is usually used in the range of 1 to 30.

The metal chelate compound of the present invention is effective as a bleaching agent for a bleaching solution or a bleach-fixing solution when it is contained in a concentration of 0.05 to 1 mol per liter of processing solution. Further, it may be contained in a small amount in a fixing solution or an intermediate bath between color development and desilvering steps. The metal chelate compound of the present invention is added to a processing solution having bleaching ability at a rate of 0.0% per liter of processing solution as described above.
It is effective to contain 5 to 1 mol, and more preferably 0.1 to 0.5 mol per liter of treatment liquid.

Next, the general formula (A) used in the present invention, (
B) and (C) will be explained in detail. General formula (A
), Q201 preferably represents an atomic group necessary to form a 5- or 6-membered heterocycle composed of at least one of carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and selenium atoms. The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle include tetrazoles, triazoles, imidazoles, thiadiazoles, oxadiazoles, selenadiazoles, oxazoles, thiazoles, benzoxazoles, benzthiazoles, benzimidazoles, and pyrimidines. , triazaindenes, tetraazaindenes, pentaazaindenes, and the like.

R201 is a carboxylic acid or its salt (eg, sodium salt, potassium salt, ammonium salt, calcium salt), sulfonic acid or its salt (eg, sodium salt, potassium salt, ammonium salt, magnesium salt, calcium salt), phosphonic acid or its salts (e.g. sodium salt, potassium salt, ammonium salt), substituted or unsubstituted amino groups (e.g. unsubstituted amino group, dimethylamino group, diethylamino group, methylamino group, bismethoxyethylamino group), substituted or unsubstituted amino group (e.g. unsubstituted amino group, dimethylamino group, diethylamino group, methylamino group, bismethoxyethylamino group), 1 to 10 carbon atoms substituted with at least one substituted ammonium group (e.g. trimethylammonium group, triethylammonium group, dimethylbenzylammonium group)
Alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, isopropyl group, 2-hydroxypropyl group, hexyl group, octyl group), alkenyl groups having 2 to 10 carbon atoms (e.g. vinyl group, propenyl group, butenyl group) group), aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group), aryl group having 6 to 12 carbon atoms (e.g. phenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, naphthyl group), carbon number It represents 1 to 10 heterocyclic groups (eg, pyridyl group, thienyl group, furyl group, triazolyl group, imidazolyl group) or a single bond. Furthermore, R201 may be a group consisting of any combination of the above-mentioned alkyl group, alkenyl group, aralkyl group, aryl group, and heterocyclic group (for example, a heterocyclic-substituted alkyl group), or -CO-, -CS- , -SO2-, -NR2
It may contain a linking group consisting of any combination of 02-, -O- or -S-. Here, R202 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, butyl group, hexyl group), an aralkyl group having 7 to 10 carbon atoms (
For example, it represents a benzyl group, a phenethyl group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group, a 4-methylphenyl group).

M201 is a cationic group (for example, a hydrogen atom,
represents an alkali metal atom such as a sodium atom or a potassium atom, an alkaline earth metal atom such as a magnesium atom or a calcium atom, or an ammonium group such as an ammonium group or a triethylammonium group).

Further, the heterocycle represented by the general formula (A) and R201 are a nitro group, a halogen atom (for example, a chlorine atom, a bromine atom), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (for example, a methyl group). , ethyl group, propyl group, t-butyl group, cyanoethyl group),
Aryl groups (e.g. phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group), alkenyl groups (e.g. allyl group), aralkyl groups (e.g. benzyl group, 4 -methylbenzyl group, phenethyl group), sulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group), carbamoyl group (e.g. unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group), sulfamoyl group (e.g. unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group), carbonamide group (e.g. acetamide group, benzamide group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group) group), acyloxy group (e.g. acetyloxy group, benzoyloxy group), sulfonyloxy group (e.g. methanesulfonyloxy group), ureido group (e.g. unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group), thioureido group groups (e.g., unsubstituted thioureido group, methylthioureido group), acyl groups (e.g., acetyl group, benzoyl group),
Oxycarbonyl group (e.g. methoxycarbonyl group, phenoxycarbonyl group), oxycarbonylamino group (
For example, it may be substituted with a methoxycarbonylamino group, a phenoxycarbonylamino group, a 2-ethylhexyloxycarbonylamino group), a hydroxyl group, or the like.

[0062] q represents an integer from 1 to 3, and when q represents 2 or 3, each R201 may be the same or different.

In general formula (A), preferably Q201 represents tetrazoles, triazoles, imidazoles, oxadiazoles, triazaindenes, tetraazaindenes, or bentazaindenes, and R201 represents a carboxylic acid or represents an alkyl group having 1 to 6 carbon atoms substituted with one or two groups selected from salts thereof, sulfonic acids, and salts thereof; q represents 1 or 2; Among general formula (A), a more preferable compound is general formula (D). General formula (D)

[0064]

[Chemical formula 33]

In the formula, M201 and R201 have the same meanings as in the general formula (A). T and U are C
-R202 or N, R202 represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carbonamide group, a sulfonamide group, a ureido group, a thioureido group, or R201 . However, when R202 represents R201, it may be the same as or different from R201 in general formula (A).

Next, general formula (D) will be explained in detail. T and U represent C-R202 or N, R202
is a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), a hydroxy group, a nitro group, an alkyl group (e.g. methyl group, ethyl group, methoxyethyl group, n-butyl group, 2-ethylhexyl group, etc.), Alkenyl groups (e.g. allyl group, etc.), aralkyl groups (e.g. benzyl group, etc.)
4-methylbenzyl group, phenethyl group, 4-methoxybenzyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, 4-methanesulfonamidophenyl group, 4-
methylphenyl group, etc.), carbonamide group (e.g.
acetylamino group, benzoylamino group, methoxybropionylamino group, etc.), sulfonamide group (e.g.
methanesulfonamide group, benzenesulfonamide group,
p-toluenesulfonamide group, etc.), ureido group (e.g., unsubstituted ureido group, methylureido group, phenylureido group, etc.), thioureido group (e.g., unsubstituted thioureido group, methylthioureido group, methoxyethylthio ureido group, phenylthioureido group, etc.)

or represents R201. However, R202
When represents R201, it may be the same as or different from R201 in general formula (A). In general formula (D), preferably T=U=N or T=U=C-R202, R202 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R201 represents a carboxylic acid or a salt thereof, a sulfone Represents an alkyl group having 1 to 4 carbon atoms substituted with one or two groups selected from acids or salts thereof. Specific examples of the compound of general formula (A) of the present invention are shown below, but the present invention is not limited thereto.

[0068]

[C34]

[0069]

[C35]

[0070]

[C36]

The compound of the general formula (A) used in the present invention is manufactured by Berichte der Deutschen Hemitschen Gesellschaft.
tschen Chemischen Gesel
lschaft) 28, 77 (1895), Japanese Patent Application Publication No. 1973
-37436, 51-3231, U.S. Patent No. 3,2
No. 95,976, U.S. Pat. No. 3,376,310, Berichte der Deutsch Hemitschen Gesellschaft.
enChemischen Gesellschaf
t) 22, 568 (1889), 29, 2483 (1
896), Journal of the American Chemical Society (J.Chem.Soc.) 1932, 1806, Journal of the American Chemical Society (J.Am.Chem.Soc.) 71, 4000 (
1949), U.S. Pat. No. 2,585,388, 2,5
No. 41,924, Advances in Heterocyclic Chemistry
Heterocyclic Chemistry)9
, 165 (1968), Organic Synthesis (O
rganic Synthesis) IV, 569 (
1963), Journal of the American Chemical Society (J.Am.Chem.Soc.)
45, 2390 (1923), Hemische Berichte (C
hemische Berichte) 9, 465 (
1876), Special Publication No. 28496 (1976), Japanese Patent Publication No. 1876 (1976)
No. 89034, U.S. Pat. No. 3,106,467, U.S. Patent No. 3,
No. 420,670, No. 2,271,229, No. 3.1
No. 37,578, No. 3,148,066, No. 3,51
No. 1,663, No. 3,060,028, No. 3,271
, No. 154, No. 3,251,691, No. 3,598,
No. 599, No. 3,148,066, Special Publication No. 43-41
No. 35, U.S. Patent No. 3,615,616, U.S. Patent No. 3,420
, No. 664, No. 3,071,465, No. 2,444,
No. 605, No. 2,444,606, No. 2,444,6
It can be synthesized according to the method described in No. 07, No. 2,935,404, etc.

Next, general formula (B) will be explained in detail. In general formula (B), Q301 is a carbon atom, a nitrogen atom,
Represents a 5- or 6-membered mesoion ring composed of an oxygen atom, a sulfur atom, or a selenium atom, and X301- is -
Represents O-, -S- or -N-R301. R301
represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group.

The mesoionic compound represented by the general formula (B) of the present invention is defined by W. Baker and W. D. Ollis Quarterly Review (Ouart.Rev.) 11
, 15 (1957), Advances in Heterocyclic Chemistry.
Heterocyclic Chemistry
) 19, 1 (1976) and is a group of compounds defined as "5- or 6-membered heterocyclic compounds that cannot be represented satisfactorily with a single covalent structural formula or polar structural formula, and Represents a compound in which all constituent atoms have a sextad of π electrons associated with the ring, which is partially positively charged, balanced by an equal negative charge on the outer ring atom or group.

Examples of the mesoionic ring represented by Q301 include imidazoliums, pyrazoliums, oxazoliums, thiazoliums, triazoliums, tetrazoliums, thiadiazoliums, oxadiazoliums, thiatriazoliums, and oxatriazoliums. Examples include the following.

R301 is a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, n-butyl, isopropyl, n-octyl, carboxymethyl, dimethylaminoethyl), a substituted or unsubstituted cycloalkyl group (for example, cyclohexyl group, 4-methylcyclohexyl group, cyclobentyl group, etc.), substituted or unsubstituted alkenyl group (e.g. propenyl group, 2-methylpropenyl group, etc.), substituted or unsubstituted alkynyl group (e.g. propargyl group, butynyl group) , 1-methylpropargyl group, etc.), substituted or unsubstituted aralkyl group (e.g. benzyl group, 4-methoxybenzyl group, etc.)
, a substituted or unsubstituted aryl group (e.g. phenyl group, naphthyl group, 4-methylphenyl group, 3-methoxyphenyl group, 4-ethoxycarbonylphenyl group, etc.),
It represents a substituted or unsubstituted heterocyclic group (eg, pyridyl group, imidazolyl group, morpholino group, triazolyl group, tetrazolyl group, thienyl group, etc.). Further, the mesoionic ring represented by M may be substituted with the substituent described in general formula (A). Further, the compound represented by the general formula (B) may be a salt (for example, an acetate, a nitrate, a salicylate,
hydrochloride, iodate, bromate).

In general formula (B), preferably X301- is -
Represents S-. Among the mesoionic compounds of general formula (B) used in the present invention, the following general formula (E) is more preferable:
can be given. General formula (E)

[0077]

[C37]

In the formula, X301 represents N or C-R303, Y301 represents O, S, N or N-R304, and Z301 represents N, N-R305 or C-R306.
represents. R302, R303, R304, R305 and R306 are alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, aryl groups, heterocyclic groups, amino groups, azilamino groups, sulfonamide groups, ureido groups, sulfamoylamino group, acyl group,
Represents a thioacyl group, carbamoyl group or thiocarbamoyl group. However, R303 and R306 may be hydrogen atoms. Also, R302, R303, R30
2 and R305, R302 and R306, R304 and R30
5 and R304 and R306 may form a ring.

The compound represented by the above general formula (E) will be explained in detail. R302, R303, R304, R
305 and R306 are substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, n-propyl group, t-
butyl group, methoxyethyl group, carboxyethyl group, carboxymethyl group, dimethylaminoethyl group, sulfoethyl group, sulfomethyl group, sulfopropyl group, aminoethyl group, methylthiomethyl group, trimethylammonioethyl group, phosphonomethyl group, phosphonoethyl group) , substituted or unsubstituted cycloalkyl groups (e.g., cyclohexyl group, cyclopentyl group, 2-methylcyclohexyl group), substituted or unsubstituted alkenyl groups (e.g., allyl group, 2-methylallyl group), substituted or unsubstituted alkynyl groups ( For example, propargyl group) substituted or unsubstituted aralkyl group (for example, benzyl group, phenethyl group, 4-sulfobenzyl group), aryl group (for example, phenyl group, naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4 -carboxyphenyl group, 4-sulfophenyl group, 3,4-disulfophenyl group), or substituted or unsubstituted heterocyclic group (e.g. 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2- thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group), substituted or unsubstituted amino group (e.g. unsubstituted amino group, dimethylamino group, methylamino group, carboxymethylamino group), acylamino group (e.g. acetylamino group, benzoylamino group, methoxypropionylamino group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, 4
-toluenesulfonamide group), ureido group (e.g.
unsubstituted ureido group, 3-methylureido group), sulfamoylamino group (e.g. unsubstituted sulfamoylamino group, 3-methylsulfamoylamino group), acyl group (e.g. acetyl group, benzoyl group), thioacyl group (e.g. thioacetyl group), carbamoyl group (e.g. unsubstituted carbamoyl group, dimethylcarbamoyl group), or thiocarbamoyl group (e.g. dimethylthiocarbamoyl group)
represents. However, R303 and R306 may be hydrogen atoms.

In general formula (E), preferably X301 is N,
represents C-R303, Y301 represents N-R304 or S, O, Z301 represents N or C-R306, R302, R303 or R306 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Represents a substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group. However, R303 and R306 may be hydrogen atoms. R304 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted thioacyl group A substituted or unsubstituted thiocarbamoyl group is preferred.

In general formula (E), more preferably X301
represents N, Y301 represents N-R304, Z3
01 represents C-R306. R302 and R304
represents an alkyl group having 1 to 6 carbon atoms, and R306 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. However, it is more preferable that at least one alkyl group among R302, R304 and R306 is substituted with at least one carboxylic acid group, sulfonic acid group, amino group, or phosphono group. Specific examples of the compound of general formula (B) of the present invention are shown below, but the present invention is not limited thereto.

[0082]

[C38]

[0083]

[C39]

[0084]

[C40]

The compound represented by the general formula (B) or (E) of the present invention is described in the Journal of Heterocyclic Chemistry (J. Heterocyclic Chemistry).
Chem. ) 2, 105 (1965), Journal
of Organic Chemistry (J.Org.Ch
em. ) 32, 2245 (1967), Journal of Chemical Society (J.Chem.Soc.
) 3799 (1969), Journal of the American Chemical Society (J.Am.Chem.S.
oc. ) 80, 1895 (1958), Chemical Communication (Chem.Commun.) 1222
(1971), Tetrahedron Letters (Tetra
hedron Lett. ) 2939 (1972),
JP-A-60-87322, Berichte der Deutsche Cheso Hemischen Gesellschaft
e der Deutschen Chemises
Chen Gesellschaft) 38, 404
9 (1905), Journal of Chemical Society Chemical Communication (J, Chem.
．． Soc. Chem. Commun. )1224(19
71), JP-A-60-122936, JP-A-60-1
No. 17240, Advances in Heterocyclic Chemistry
eterocyclic chemistry)19
, 1 (1976), Tetrahedron Letters (Tet
rahedron Letters) 5881 (19
68), Journal of Heterocyclic Chemistry (J. HeterocyclicChem.)
5, 277 (1968), Journal of the Chemical Society Parkin Transactions I (J.
Chem. Soc. , PerkinTrans. I)6
27 (1974), Tetrahedron Letters (Tet
rahedron Letters) 1809 (19
67), 1578 (1971), Journal of
Chemical Society (J.Chem.Soc.) 8
99 (1935), 2865 (1959), Journal of Organic Chemistry (J.Org.
Chem. ) 30, 567 (1965).

Next, general formula (C) will be explained in detail. L401 and L403 are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms (e.g., methyl group, ethyl group,
propyl group, hexyl group, isopropyl group, carboxyethyl group, etc.), substituted or unsubstituted, with 6 to 12 carbon atoms
aryl group (e.g., phenyl group, 4-methylphenyl group, 3-methoxyphenyl group, etc.), substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, etc.), or Substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, (e.g. vinyl group,
propenyl group, 1-methylvinyl group, etc.) or a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms (e.g.,
Pyridyl group, furyl group, thienyl group, imidazolyl group,
etc.), and L402 represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms (e.g., methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1-methylethylene group, 1
-hydroxytrimethylene group, etc.), substituted or unsubstituted arylene group having 6 to 12 carbon atoms (e.g. phenylene group, naphthylene group, etc.), substituted or unsubstituted aralkylene group having 7 to 12 carbon atoms (e.g. 1 , 2-xylylene group, etc.), a substituted or unsubstituted heterocyclic linking group having 1 to 10 carbon atoms (e.g.

[0087]

[C41]

A401 and B401 are -S-, -O-,
-NR420-, -CO-, -CS-, -SO2- or any combination thereof; examples of arbitrary combinations include -CONR421-, -NR422C
O-, -NR423CONR424-, -COO-, -
OCO-, -SO2NR425-, -NR426SO2
-, -CSNR427-, -NR428CS-, -NR
429CONR430- and the like.

[0089] r represents an integer from 1 to 10. However, L
At least one of 401 and L403 is -SO9M40
1, -PO9M402M403, -NR401 (R40
2) (It may be in the form of a salt such as hydrochloride or acetate; for example, unsubstituted amino group, methylamino group, dimethylamino group, N
-methyl-N-hydroxyethylamino group, N-ethyl-N-carboxyethylamino group, etc.), -N+R40
3(R404)(R405)・X401- (e.g., trimethylammoniochloride group, etc.), -SO2NR4
06 (R407) (e.g., unsubstituted sulfamoyl group,
dimethylsulfamoyl group, etc.), -NR408SO2
R409 (e.g. methanesulfonamide group, benzenesulfonamide group, etc.), -CONR410 (R411
) (e.g., unsubstituted carbamoyl group, N-methylcarbamoyl group, N,N-bis(hydroxyethyl)carbamoyl group, etc.), -NR412COR413 (e.g., formamide group, acetamido group, 4-methylbenzoylamino group, etc.) , -SO2R14 (e.g. methanesulfonyl group, 4-chlorophenylsulfonyl group, etc.), -
PO(-NR415(R416)2 (e.g., unsubstituted phosphonamide group, tetramethylphosphonamide group, etc.)
, -NR417CONR418 (R419) (e.g.
unsubstituted ureido group, N,N-dimethylureido group, etc.)
, heterocyclic groups (e.g. pyridyl group, imidazolyl group,
thienyl group, tetrahydrofuranyl group, etc.) -COOM
404.

M401, M402, M403 and M40
4 represents a hydrogen atom or a counter cation (for example, an alkali metal atom such as a sodium atom or a potassium atom, an alkaline earth metal atom such as a magnesium atom or a calcium atom, an ammonium group such as ammonium or triethylammonium, etc.) .

R401 to R430 are hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, hexyl group, isopropyl group, etc.), substituted or unsubstituted carbon atoms Aryl groups having 6 to 12 carbon atoms (e.g. phenyl group, 4-methylphenyl group, 3-methoxyphenyl group, etc.), substituted or unsubstituted aralkyl groups having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, etc.) or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms (e.g., vinyl group, propenyl group, 1-methylvinyl group, etc.), and X- represents a counter anion (e.g., chlorine ion, bromide ion, etc.). halogen ion, nitrate ion, sulfate ion, acetate ion, p-toluenesulfonate ion, etc.).

0092 L401, L402, L403, R401
When each group of ~R430 has a substituent, the substituent includes a lower alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, etc.), an aryl group having 6 to 10 carbon atoms (e.g., phenyl, 4-methylphenyl group, etc.), carbon number 7
~10 aralkyl groups (e.g. benzyl group, etc.), C2-C4 alkenyl groups (e.g. propenyl group, etc.)
, an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group,
ethoxy group, etc.), halogen atom (e.g. chlorine atom,
bromine atom, etc.), cyano group, nitro group, carboxylic acid group (
(may be in the form of a salt), hydroxyl group, etc. However, when r is 2 or more, A401 and L402 may be any combination of the groups listed above. Also, A401, B4
At least one of 01 represents -S-.

In general formula (C), preferably L401 and L
At least one of 403 is -SO3M401, -PO3
M402M403, -NR401 (R402), -N+
R403 (R404) (R405). A401 and B401 are -S- -O
- or -NR420-, R401, R402
, R403, R404, R405 and R420 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r is 1 to 6.
Represents an integer of 6. In general formula (C), more preferably L
401 and L403 are -SO3M401, -PO3M4
02M403-COOM404 substituted carbon number 1~
4, and A401 and B401 are -S-
, and r represents an integer from 1 to 3. Specific examples of the compounds of the present invention are shown below, but the present invention is not limited thereto.

[0094]

[C42]

[0095]

[C43]

[0096]

[C44]

[0097]

[C45]

The compound represented by the general formula (C) of the present invention is described in Journal of Organic Chemistry (J.Org.Chem.) 30, 2867 (1965
), 27, 2846 (1962), Journal of the American Chemical Society (J.Am.C.
hem. Soc. ) 69, 2330 (1947) etc., it can be easily synthesized.

The compound represented by the general formula (Dev) will be explained in detail below. In the general formula (Dev), R1 and R3 each represent an alkyl group having 1 to 4 carbon atoms, and R2 represents a linear or branched alkylene group having 3 or 4 carbon atoms. Specific examples of R1 and R3 include methyl group, ethyl group, propyl group, isopropyl group,
Examples include butyl group, (sec)butyl group, and the like. Further, specific examples of R2 include propylene group, butylene group, 1-methylethylene group, 2-methylethylene group, 1-methylethylene group,
Examples include methylpropylene group, 2-methylpropylene group, and 3-methylpropylene group. General formula (Dev)
Among them, R1 preferably represents an ethyl group or a propyl group,
R3 preferably represents a methyl group or an ethyl group. The main chain of R2 is preferably a propylene group or a butylene group, and preferably a butylene group. General formula (Dev)
Since the compound represented by is extremely unstable when stored as a free amine, it is generally manufactured and stored as an inorganic or organic salt, and only becomes a free amine when added to the processing solution. preferable. General formula (De
Examples of inorganic and organic acids for forming salts of the compound (v) include hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, and naphthalene-1,5-disulfonic acid. Specific examples of the compounds of the present invention are shown below, but the present invention is not limited thereto.

[0100]

[C46]

[0101]

[C47]

[0102]

[C48]

The color developing agent of the present invention can be easily synthesized according to the method described in Journal of the American Chemical Society, Vol. 73, 3100 (1951).

The color developing agent of the present invention is preferably used alone or in combination with other known p-phenylenediamine derivatives. Examples of compounds that can be combined are described below.

The image forming system including the usable photosensitive materials and processing of the present invention can be applied to commonly used photosensitive materials, such as black and white photosensitive materials for printing, medical and general use, color negatives, color reversal and color photosensitive materials. It can be used to process color photosensitive materials such as paper. Among these, for example, it can be used to process color prints to take advantage of its speed, but it can also be used for intelligent color hard copy applications where speed is more desired. In particular, as an embodiment of the intelligent color hard copy, an embodiment 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.

Silver halides used in the light-sensitive material according to the present invention include silver chloride, silver bromide, (iodine) silver chlorobromide,
Silver iodobromide etc. can be used, but especially for the purpose of rapid processing, silver chloride containing substantially no silver iodide can be used.
It is preferred to use silver chlorobromide or silver chloride emulsions with a mole % or more, more preferably 95% or more, particularly 98% or more.

[0107] In the photosensitive material according to the present invention, for the purpose of improving image sharpness, etc., the hydrophilic colloid layer contains compounds such as those described in European Patent No. EP 0,337,490A2, No. 27 to
Adding dyes (especially oxonol dyes) that can be decolorized by the treatment described on page 76 so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide that has been surface-treated with a di- to tetrahydric alcohol (for example, trimethylolethane).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277,589A2 together with a coupler. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. The use of a compound that chemically combines with the oxidized form of a group amine color developing agent to form a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, to reduce the amount remaining in the film during storage after processing. This is preferable in order to prevent the generation of stains and other side effects due to the formation of color pigments due to the reaction between the color developing agent or its oxidized product and the coupler.

[0110] Furthermore, the photosensitive material according to the present invention has a preventive agent as described in JP-A No. 63-271247 in order to prevent various types of mold and bacteria that propagate in the hydrophilic colloid layer and cause image deterioration. It is preferable to add a fungicide.

[0111] The support used in the light-sensitive material according to the present invention may be a white polyester support for display purposes or a layer containing a white pigment provided on the support on the side having a silver halide emulsion layer. A support may also be used. In order to further improve the sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support. In particular, the transmission density of the support was set to 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferable to set it in the range of 5 to 0.8.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-intensity exposure or high-intensity short-time exposure, and particularly in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 -4 seconds is preferred.

The exposed photosensitive material may be subjected to color development, but for the purpose of rapid processing, it is preferable to carry out bleach-fixing after color development. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution is preferably about 5 or less, more preferably about 4.0 or less, for the purpose of promoting desilvering.

[0114] The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and the processing method applied to process this light-sensitive material. As processing additives, the following patent publications, especially European patent EP 0,355,660A2
Those described in the specification of Japanese Patent Application No. 1-107011 are preferably used.

[0115]

[Table 1]

[0116]

[Table 2]

[0117]

[Table 3]

[0118]

[Table 4]

[0119]

[Table 5] As cyan couplers, in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, the 3-hydroxypyridine cyan coupler described in European Patent EP 0,333,185A2 ( Particularly preferred are couplers (6) and (9), which are made by adding a chlorine leaving group to a 4-equivalent coupler (4-equivalent coupler (42) listed as a specific example), and couplers (6) and (9).
It is also preferable to use the cyclic active methylene cyan couplers described in Japanese Patent No. 4-32260 (particularly preferred are coupler examples 3, 8, and 34 listed as specific examples).

In the present invention, a color developer or a black and white developer is used as the developer. The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-1 N,N-diethyl-p-phenylenediamine D-2 4-amino-N,N-diethyl-3-methylaniline D-3 4-amino-N-(β-hydroxyethyl)
-N-Methylaniline D-4 4-Amino-N-ethyl-N-(β-hydroxyethyl)aniline D-5 4-Amino-N-ethyl-N-(β-hydroxyethyl)-3-methylaniline D -6 4-Amino-N-ethyl-N-(3-hydroxypropyl)-3-methylaniline D-7 4-amino-N-ethyl-N-(4-hydroxybutyl)-3-methylaniline D-8 4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-3-methylaniline D-9
4-amino-N,N-diethyl-3-(β-hydroxyethyl)aniline D-10 4-amino-N-ethyl-N-(β-methoxyethyl)-3methyl-aniline D-11 4-amino- N-(β-ethoxyethyl)
-N-Ethyl-3-methylaniline D-12 4-Amino-N-(3-carbamoylpropyl-N-n-propyl-3-methylaniline D-13
4-amino-N-(4-carbamoylbutyl-N-
n-propyl-3-methylaniline D-14 N-(
4-Amino-3-methylphenyl)-3-hydroxypyrrolidine D-15 N-(4-amino-3-methylphenyl)
-3-(hydroxymethyl)pyrrolidine D-16 N-(4-amino-3-methylphenyl)
-3-pyrrolidinecarboxamide Among the above p-phenylenediamine derivatives, particularly preferred are exemplary compounds D-5, D-6, D-7, D-8 and D-
It is 12. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid, etc. may also be used. The amount of the aromatic primary amine developing agent used is preferably 0.002 mol to 0.2 mol per liter of developer,
More preferably 0.005 mol to 0.15 mol, still more preferably 0.01 mol to 0.15 mol.

[0122] In carrying out the present invention, it is preferable to use a developer containing substantially no benzyl alcohol. Here, "substantially not containing" preferably means 2
The benzyl alcohol concentration is less than or equal to milliliter/liter, more preferably less than 0.5 milliliter/liter, and most preferably, it contains no benzyl alcohol at all.

[0123] It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency. This kind of effect is
This is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0 x 10 -3 mol/liter or less, and most preferably no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably contains substantially no sulfite ions, and more preferably substantially no hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties. The expression "substantially not containing hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0 x 10-3 mol/liter or less, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion. The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, they are organic compounds that have the function of preventing oxidation of color developing agents by air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter), hydroxamic acids, hydrazines,
Hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed rings Formula amines are particularly effective organic preservatives. These are JP-A-63-4235 and JP-A-63-30.
No. 845, No. 63-21647, No. 63-44655
No. 63-53551, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-
No. 43138, No. 63-146041, No. 63-44
No. 657, No. 63-44656, U.S. Patent No. 3,61
No. 5,503, No. 2,494,903, Japanese Unexamined Patent Publication No. 1973-
It is disclosed in various publications or specifications such as No. 143020 and Japanese Patent Publication No. 48-30496.

[0126] Other preservatives include JP-A-57-441
48 and 57-53749, salicylic acids as described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, JP-A-56- Polyethyleneimines described in Japanese Patent No. 94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, etc. may be contained as necessary. In particular, it is preferable to add alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred, and details thereof can be found in JP-A-1-97953, JP-A-1-186939, and JP-A-1-1-1. 1
It is described in No. 86940, No. 1-187557, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

[0129] As the above-mentioned amines, JP-A-63-2
Cyclic amines such as those described in JP-A No. 39447, amines such as those described in JP-A-63-128340, and other amines such as those described in JP-A-1-186939 and JP-A-1-187.
Examples include amines such as those described in Japanese Patent No. 557.

In the present invention, it is preferred that the color developer contains 3.5 x 10-2 to 1.5 x 10-1 mol/liter of chlorine ions. Particularly preferably, 4×10
-2 to 1×10 −1 mol/liter. If the chloride ion concentration is more than 1.5 x 10-1 mol/liter, it has the disadvantage of retarding development, which is not preferable in achieving the object of the present invention, which is rapid development and a high maximum concentration. Moreover, if it is less than 3.5×10 −2 mol/liter, it is not preferable in terms of preventing fogging.

In the present invention, the content of bromine ions in the color developer is preferably 1.0 x 10-3 mol/liter or less. More preferably, it is 5×10 −4 mol/liter or less. Bromine ion concentration is 1 x 10-3 mol/
More than liters will retard development and reduce maximum density and sensitivity.

[0132] Here, the chloride ions and bromine ions may be directly added to the developer, or may be eluted from the light-sensitive material into the developer during the development process. When added directly to color developers, sodium chloride,
Examples include potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred are sodium chloride and potassium chloride.

[0133] Alternatively, the brightening agent may be supplied from a fluorescent brightener added to the developer. Sodium bromide, potassium bromide, ammonium bromide,
Examples include lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, and thallium bromide, of which potassium bromide and sodium bromide are preferred.

[0134] When eluted from the photosensitive material during the development process,
Both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion. The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and may contain other compounds as known developer components. .

[0135] In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate,
Glycyl salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-
Amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high pH range of pH 9.0 or higher, and even when added to color developers, they have no effect on photographic performance. It is particularly preferable to use these buffers because they have the advantages of having no adverse effects (fogging, etc.) and being inexpensive.

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-2
-potassium hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

[0137] The amount of the buffer added to the color developer is 0.
．． It is preferably 1 mol/liter or more, especially 0
．． Particularly preferred is 1 mol/liter to 0.4 mol/liter.

[0138] In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or in order to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N
',N'-tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid , 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-
Examples include hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

[0140] Any development accelerator can be added to the color developer if necessary. As a development accelerator,
-16088, 37-5987, 38-782
6, No. 44-12380, No. 45-9019, and U.S. Pat.
p expressed in No. 829 and No. 50-15554
- Phenylenediamine compound, JP-A-50-1377
No. 26, Special Publication No. 44-30074, Japanese Patent Publication No. 56-15
Quaternary ammonium salts disclosed in No. 6826 and No. 52-43429, etc., U.S. Patent No. 2,494,90
No. 3, No. 3,128,182, No. 4,230,796
No. 3,253,919. Tokuko Sho 41-11431
No. 2,482,546, U.S. Patent No. 2,596,
Amine compounds described in each publication or specification such as No. 926 and No. 3,582,346, Japanese Patent Publication No. 37-16088
No. 42-25201, U.S. Patent No. 3,128,1
No. 83, Special Publication No. 11431, No. 42-2388
Polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, etc. described in publications or specifications such as No. 3 and U.S. Patent No. 3,532,501 can be added as necessary. .

[0141] In the present invention, any antifoggant can be added as required. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

[0142] Color developers applicable to the present invention include:
Preferably, it contains an optical brightener. As the fluorescent brightener, 4,4'-diamino-2,2'-dizulfostilbene compounds are preferred. The amount added is 0 to 5 g/liter, preferably 0.1 to 4 g/liter.

[0143] Also, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, aromatic carboxylic acids, etc. may be added as necessary. The processing temperature of the color developer applicable to the present invention is 30 to 50°C, preferably 35 to 50°C. The treatment time is 5 seconds to 30 seconds, preferably 5 seconds to 20 seconds, and more preferably 5 to 15 seconds. It is preferable that the amount of replenishment is small, but 20 to 600 ml per 1 m2 of photosensitive material is appropriate, and preferably 30 to 1 ml.
00ml.

The black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. can be used alone or in combination.

[0145] The pH of these black and white developers is generally 9-9.
It is 12. The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below. As the bleaching agent used in the bleaching solution or bleach-fixing solution, any bleaching agent can be used, but in particular organic complex salts of iron (III) (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) 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; hydrogen peroxide and the like are preferred. More preferred are the compounds listed in claim 2 of the present invention.

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. iron(
The aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming the organic complex salt of III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid. , propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, iron(III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid 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.
In a solution, iron, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc., and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. are used. A diiron ion complex salt may be formed. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.
0 mol/liter, preferably 0.05 to 0.50 mol/liter, more preferably 0.10 to 0.50 mol/liter
liter, more preferably 0.15 to 0.40 mol/liter.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, as described in U.S. Pat. Compounds having a mercapto group or disulfide bond, Japanese Patent Publication Nos. 45-8506, 52-20832, 5
Thiourea compounds described in No. 3-32735 and US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions that can be applied to the present invention include bromides (for example, potassium bromide, sodium bromide, ammonium bromide) or chlorides (for example, potassium chloride, sodium chloride, ammonium chloride). )
or a rehalogenating agent such as an iodide (eg, ammonium iodide). If desired, 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, etc. Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

[0149] The pH range of the bleach-fix solution in the present invention is 5.
The number is as follows, preferably 2 to 5, and particularly preferably 3 to 4. If the pH is lower than this, leucoization of the cyan dye will be promoted and at the same time, the solution will deteriorate. Furthermore, if the pH is higher than this, the fixing speed is delayed and stains are more likely to occur.

To adjust the pH, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

[0151] It is preferable that the stirring of the nuclear treatment solution in the desilvering step be as strong as possible from the viewpoint of shortening the desilvering treatment time and improving alcohol content. As a stirring means, JP-A-62-1834 is used.
60 and No. 62-183461, etc., and in the case of a means of colliding jets, the time until collision is 10 minutes after the photosensitive material is introduced into the processing solution.
It is preferable to do this within In the present invention, the crossover time from the color developer to the bleach-fix solution (the time in the air from when the photosensitive material leaves the color developer to when it enters the bleach-fix solution) improves bleach fog and dirt adhesion on the surface of the photosensitive material. The time is preferably within 10 seconds. In addition, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants,
Organic solvents such as polyvinylpyrrolidone and methanol can be contained. Bleach-fix solutions and bleaching solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), It is preferred to include a sulfite ion releasing compound such as a metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). The content of these compounds is preferably about 0.02 to 1.0 mol/liter, more preferably 0.04 to 0.6 in terms of sulfite ion.
mole/liter.

[0152] As a preservative, sulfites are generally added, but other substances such as ascorbic acid, carbonyl bisulfite adducts, or carbonyl compounds may also be added. Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as desired.

[0153] The bleach-fix solution of the present invention has a processing time of 5 seconds to 12 seconds.
0 seconds, preferably 10 seconds to 60 seconds. The processing temperature is 2
The temperature is 5°C to 60°C, preferably 30°C to 50°C. In addition, the replenishment amount is 20ml to 250ml per 1m2 of photosensitive material.
, preferably 30 ml to 100 ml. Preservatives include sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. It is preferred to contain a sulfite ion releasing compound such as potassium bisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of about 0.02 to 1.0 mol/liter, more preferably 0.04 to 0.6 mol/liter, in terms of sulfite ions.

[0154] As a preservative, sulfites are generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added.

[0155] Furthermore, buffering agents, optical brighteners, chelating agents,
Antifoaming agents, antifungal agents, etc. may be added as desired. After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of washing water in the washing step can be set within a wide range depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (number of stages), and various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the
Society of Motion Picture and
Television Engineers (Journal o
f the Society of Moti
on Picture and Televis
ion Engineers) Volume 64, p. 248-2
53 (May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 5.

[0157] According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, to 500 ml or less per 1 m2 of photosensitive material, and the effect of the present invention is remarkable.
The increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to such problems, JP-A-62-2
The method for reducing calcium and magnesium described in Japanese Patent No. 88838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542, JP-A No. 61-1201
Chlorine-based disinfectants such as chlorinated sodium isocyanurate described in Publication No. 45, benzotriazole, copper ion, etc. described in JP-A No. 61-267761, and others such as "Chemistry of Anti-Mold" by Hiroshi Horiguchi (1986) 1982) Sankyo Publishing, edited by Hygiene Technology Society, "Microbial Sterilization, Sterilization, and Anti-Mold Technology" (1982), "Encyclopedia of Antibacterial and Antifungal Agents", edited by Society of Industrial Engineers, Japan Antibacterial and Antifungal Society.
(1986) can also be used.

Furthermore, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used. Continue with the above washing process or
Alternatively, it is also possible to directly treat with a stabilizing solution without going through a water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

[0159] Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step,
JP-A-57-8543, JP-A No. 58-14834, JP-A No. 6
All known methods described in JP 0-220345 and the like can be used.

Others: 1-hydroxyethylidene-1,
It is also a preferred embodiment to use a chelating agent such as 1-diphosphonic acid or ethylenediaminetemethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing solution can also be used as a washing solution or a stabilizing solution used after the desilvering treatment. The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the photosensitive material, it is generally 20°C to 50°C, preferably 25°C to 45°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably it is 10 seconds to 60 seconds, more preferably 15 seconds to 45 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specifically preferred amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Alternatively, the amount is 500 ml or less, preferably 300 ml or less per m2 of photosensitive material. Further, replenishment may be performed continuously or intermittently. The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage counter-current system to reduce the overflow of the wash water into a bleach-fix bath, which is a pre-bath, and replenish the bleach-fix bath with concentrated liquid.

The present invention aims at stable and rapid processing, and the preferred processing time from the start of the developing process to the end of the drying process is within 120 seconds. More preferably, it is within 90 seconds.

[0164] One embodiment of the present invention will be described. However, the present invention is not limited to this embodiment, and all modifications are possible based on the technical idea of the present invention.

[0165] In this process, a color paper exposed to light based on a positive original is developed, bleach-fixed, washed with water (rinsed), and then dried to form an image on the color paper. Color paper (hereinafter referred to as photosensitive material) processed by this processing apparatus is color-developed with a color developer containing an aromatic primary amine color developing agent.

[0166]

【Example】

Example 1 Preparation of Sample 1 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzene sulfonate was applied, and various photographic constituent layers were further applied. A multilayer color photographic paper (sample 1) having the layer structure shown in FIG. The coating solution was prepared as follows.

Fifth layer coating solution preparation Cyan coupler (Exc) 32.0g, color image stabilizer (C
pd-2) 3.0g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.08 g, and color image stabilizer (Cpd-
8) To 5.0g, add 50.0cc of ethyl acetate and solvent (
Solv-6) 14.0g was added and dissolved, and this solution was mixed with 20g of sodium dodecylbenzenesulfonate containing 8cc.
% gelatin aqueous solution and then emulsified and dispersed using an ultrasonic homogenizer to prepare an emulsified dispersion. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.58
A 1:4 mixture (Ag molar ratio) of a large size emulsion of μm and a small size emulsion of 0.45 μm. The coefficient of variation of grain size distribution is 0.09 and 0.11, and silver bromide is 0 for each size emulsion.
．． (6 mol% locally contained on a part of the particle surface) was prepared. This emulsion contains red-sensitive sensitizing dye E shown below at a rate of 0.9 x 10-
4 mol, and for small size emulsions, 1.1 x 10-
4 moles were added. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the composition shown below.

Coating solutions for the first to fourth, sixth and seventh layers were also prepared in the same manner as the fifth layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

[0169] In addition, Cpd-10 and Cpd-11 were added to each layer.
The total amount is 25.0mg/m2 and 50.0mg/m2 respectively.
m2 was added. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.

That is, in the blue-sensitive emulsion layer, sensitizing dye A and sensitizing dye B were added per mole of silver halide, 2.0 x 10-4 mole each for large-sized emulsions, and 2.0 x 10-4 moles each for small-sized emulsions. 2.5 x 10-4 mol each,

0171
]

embedded image In the green-sensitive emulsion layer, sensitizing dye C is added per mole of silver halide, 4.0×10 −4 mole for large emulsion, 5.6×10 for small emulsion. -4 mol and sensitizing dye D per mol of silver halide, 7.0 x 10-5 mol for large size emulsions and 1.0 x 10-5 mol for small size emulsions. ,

[0172]

[Chemical formula 50] In the red-sensitive emulsion layer, sensitizing dye E is added per mol of silver halide, 0.9 x 10-4 mol for large emulsions and 1.1 x 10 mol for small emulsions. -4 mol each were added.

[0173]

[Image Omitted] Furthermore, the following compound H was added in an amount of 2.0% per mole of silver halide.
6 x 10-3 moles were added.

[0174]

[Chemical formula 52] In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at 8% per mole of silver halide.
．． 5 x 10-5 mol, 7.7 x 10-4 mol, 2.5 x
10-4 mol was added.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added per mole of silver halide, respectively.
1 x 10-4 mol and 2 x 10-4 mol were added. In addition, the following dyes (coating amounts are shown in parentheses) were added to the emulsion layer to prevent irradiation.

[0176]

embedded image (Layer structure) The composition of each layer is shown below. The number is the coating amount (g
/m2). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain) A large size emulsion with a size of 0.88μm and a small size emulsion with a size of 0.70μm.
3:7 mixture (silver molar ratio). particle size distribution
The coefficient of variation is 0.88 and 0.10, respectively.
Each size emulsion contained 0.3 mol% silver bromide locally on a part of the grain surface)
0.25 Gelatin
1.07
Yellow coupler (ExY)
0.62 Color image stabilizer (Cpd-1)
0.19 Solvent (Solv-3)
0.1
8 Solvent (Solv-7)
0.18
Color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin
1.25
Color mixing inhibitor (Cpd-5)
0.08 Solvent (Sol
v-1)
0.16 Solvent (Solv-4)
0
．． 08 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1:3 mixture (silver molar ratio) of a large emulsion with an average grain size of 0.55 μm and a small emulsion with an average grain size of 0.39 μm. Grains rhinoceros
The coefficient of variation of the Z distribution is 0.10 and 0.08, respectively.
, each size emulsion had AgBr0.
(8 mol% was locally contained in a part of the particle surface) 0.12
gelatin
1.24 Magenta coupler (ExM) 0.1
7 Color image stabilizer (Cpd-2)
0.03
Color image stabilizer (Cpd-3)
0.16 Color image stabilizer (C
pd-4) 0.
02 Color image stabilizer (Cpd-9)
0.02
Solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin
1.42
Ultraviolet absorber (UV-1)
0.47 Color mixing prevention agent (
Cpd-5) 0
．． 05 Solvent (Solv-5)
0.24
Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1:4 mixture (silver molar ratio) of a large emulsion with an average grain size of 0.58 μm and a small emulsion with an average grain size of 0.45 μm. particle rhinoceros
The coefficient of variation of the size distribution is 0.09 and 0.11, and each size emulsion contains 0.6 mol% AgBr.
localized on a part of the particle surface) 0.2
0 gelatin
0.91
Cyan coupler (ExC)
0.35 Color image stabilizer (C
pd-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)
0.0
Solvent (Solv-6)
0.14 Sixth layer (ultraviolet absorption layer) Gelatin
0.48
Ultraviolet absorber (UV-1)
0.16 Color mixing prevention agent (Cp
d-5) 0.0
2 Solvent (Solv-5)
0.08
Seventh layer (protective layer) Gelatin
1.12
polyvinyl alcohol acrylic
Modified copolymer (degree of modification 17%) 0
．． 17 Liquid paraffin
0.03

[0178]

[C54]

[0179]

[C55]

[0180]

[C56]

[0181]

[C57]

[0182]

[C58]

[0183]

[C59]

[0184]

[C60]

[0185]

[C61]

[0186] After cutting the samples prepared as described above, each sample was measured with a sensitometer (manufactured by Fuji Photo Film Co., Ltd., model FW,
A color temperature of the light source (3200°K) was used to provide gradation exposure of a three-color separation filter for sensitometry. After exposure, the following processing steps were performed. After that, a sample exposed to white light was prepared and subjected to the same processing steps.

[0187]

Color developer water

700 ml Sodium triisopropylnaphthalene (β) sulfonate
0.1 g ethylenediaminetetraacetic acid

3.0 g 1,2-dihydroxybenzene-4,6 disulfonic acid dina
0.5 g thorium triethanolamine

12.0 g potassium chloride

10.0 g potassium bromide
0
．． 03g potassium carbonate

27.0 g Optical brightener (
WHITEX 4B (manufactured by Sumitomo Chemical)
1.0 g sodium sulfite
0.1 g
Disodium-N,N-bis(sulfonatoethyl)hydride 10.0 g Roxylamine N-ethyl-N-(β-methanesulfonamidoethyl)-9.5 g 3-
Methyl-4-aminoaniline sulfate with water
1000
ml pH (25℃)

10.35

Bleach-fix water

500ml fixing agent (see Table 6)
0.5 mole
ammonium sulfite

40 g (Use only if the fixing agent is ammonium thiosulfate) Bleach (see Table 6)
0.15 mol Chelating agent (similar to bleach)
0.02 mol ammonium chloride

42 g acetic acid (50%)

Add 116ml water
1000
ml pH (25℃) (adjusted with acetic acid and aqueous ammonia) 3.8

01
90] Rinse solution Ion exchange water (3 parts each of calcium and magnesium)
ppm or less)

[Evaluation of Desilvering Performance] After the treatment, the amount of residual silver was measured for the white exposed film of the processed sample using a fluorescent X-ray analyzer.

[Evaluation of bleaching fog] The minimum magenta density (Dmin) of the post-processed sample (imagewise exposed film) was measured using a photographic densitometer FSD103 manufactured by Fuji Photo Film Co., Ltd.

[Evaluation of image stain] After the processed sample (imagewise exposed film) was stored in a constant temperature and humidity chamber at 60°C and 70% humidity for 7 days, the minimum magenta density of the sample was evaluated. It was measured. The increase in magenta density before and after storage was expressed as ΔDmin.

[Evaluation of image density] The maximum cyan density (Dmax) of the post-processed sample (imagewise exposed film) was measured using a photographic densitometer FSD103 manufactured by Fuji Photo Film Co., Ltd.

[Evaluation of Liquid Stability] The bleach-fix solution after running treatment was visually inspected for the presence or absence of precipitation. The evaluation was determined based on the following criteria. No precipitation: ○, Small amount of precipitation: △, Large amount of precipitation: The results are shown in Table 6.

[Table 6]

As can be seen from Table 6, according to the present invention, even in a short bleach-fixing time, the desilvering property, bleaching fog,
It can be seen that good results are obtained in terms of the stability of the bleach-fix solution.

Example 2 In Example 1, the bleaching agent was changed to 1,3-diaminopropanetetraacetic acid (hereinafter abbreviated as 1,3PDTA), the bleach-fixing time was set to 10 seconds, and the pH of the bleach-fixing solution was adjusted to the values shown in Table 7. The same test as in Example 1 was conducted except for the following changes. The results are shown in Table 7.

[0198]

[Table 7]

As can be seen from Table 7, according to the present invention, even in a short bleaching time, the desilvering property, bleaching fog,
It can be seen that good results can be obtained in both image density and liquid stability.

Example 3 Same as Example 1 except that the bleaching agent in Example 1 was changed to 1,3-PDTA, the pH of the bleach-fixing solution was adjusted to 3.0, and the bleach-fixing time was changed as shown in Table 8. I did the processing. The results are shown in Table 8.

[0201]

[Table 8] As can be seen from Table 8, it is possible to desilver in a short time, the image density is high, and the bleaching fog is small.

Example 4 In Example 2, the bleaching agent was mixed with compound No. 1 and No. 21 of Fe.
(III) The same process as in Example 2 was carried out except that the pH of the bleach-fix solution was changed to 3.0 in place of salt. Table 9 shows the results.
Shown below.

[0203]

[Table 9] As can be seen from Table 9, good results can be obtained by using the bleaching agent of the present invention.

Example 5 In Example 4, the No. 1 bleaching agent was changed to -2, 3, 5, 11
, 12, 25, 26, 33, 35, 39 FE (III
), and the same treatment as in Example 4 was performed. As a result, similar to Example 4, good results were obtained.

Example 6 In Example 2, the color developing agent was replaced with Compound I-
1, I-12 and the pH of the bleach fixing agent in Table 10
The same process as in Example 1 was performed except for the following changes. The results are shown in Table 10.

[0206]

Table 10 As can be seen from Table 10, even when a color developing agent suitable for rapid development processing was used, good results with little image staining were obtained according to the present invention.

Claims (4)

[Claims] Claim 1: A processing method in which a silver halide color photographic light-sensitive material having at least one light-sensitive halide emulsion layer on a support is subjected to color development and bleach-fixing after exposure, which contains 90 mol% or more of silver chloride. A silver halide color photographic light-sensitive material containing at least one compound of the following general formula (A), (B) or (C), and p
1. A method for processing a silver halide color photographic light-sensitive material, which comprises carrying out a bleach-fixing process within 25 seconds using a bleach-fix solution in which H is 2 or more and 5 or less. General Formula (A) embedded image In the formula, Q201 represents an atomic group necessary to form a 5- or 6-membered heterocycle. Further, this heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring. R201 is a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or a monocyclic group substituted with at least one of an amino group or an ammonium salt. Represents a bond. q represents an integer of 1 to 3, and M201 represents a cationic group. General formula (B) [Chemical formula 2] In the formula, Q301 represents a 5- or 6-membered mesoion ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom, and X301- is -O-, -S-
or -N-R301. R301 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. General formula (C) L401-(A40
1-L402) r-A402-L403 where L401
and L403 may be the same or different and each represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a heterocyclic group, and L402 is an alkylene group, an arylene group, an aralkylene group, a heterocyclic linking group, or a linkage of a combination thereof. represents a group. A401 and A402
may be the same or different, respectively -S-, -O-, -
Represents NR420-, -CO-, -CS-, -SO2- or any combination thereof. r represents an integer of 1 to 10. However, L401 and L4
At least one of 03 is -SO3M401, -PO3M
402M403, -NR401 (R402), -N+R
403(R404)(R405)・X401-,-SO
2NR406 (R407), -NR408SO2R40
9, -CONR410 (R411), -NR412CO
R413, -SO2R414, -PO(-NR415(
R416))2, -NR417CONR418(R41
9), -COOM404 or a heterocyclic group. M401, M402, M403 and M
404 may be the same or different and each represents a hydrogen atom or a counter cation. M401 to M402 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group,
It represents an aralkyl group or an alkenyl group, and X401- represents a counter anion. However, at least one of A401 and A402 represents -S-. Claim 2: The bleach-fixing solution has the following general formula (I), (I
2. The silver halide color photographic light-sensitive material according to claim 1, which contains at least one metal chelating compound consisting of a compound represented by I), (III), (IV) or (V). processing method. General formula (I) [Formula 3] In the formula, X is -CO-N(OH)-Ra, -N(OH)-
CO-Rb (here, 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), -SO2NRc (Rd
) or -N(Re)SO2Rf (where Rc, Rd and Re represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Rf represents an aliphatic group, an aromatic group or a heterocyclic group). ) represents. L1 represents a divalent linking group containing an aliphatic group, an aromatic group, a heterocyclic group, or a group consisting of a combination thereof. R11 and R12 may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. General formula (II) embedded image In the formula, R21 has the same meaning as R11 in general formula (I). R
2a and R2b may be the same or different, and each -
Y1-C(=X1)-N(Rh)-Rg or -Y2-
N(Ri)-C(=X2)-Rj (where Y1 and Y
2 has the same meaning as L1 in general formula (I). Rg, Rh and Ri have the same meanings as Ra in general formula (I). Rj is an aliphatic group, an aromatic group, a heterocyclic group, -NRk (R1) (where Rk and R1 have the same meaning as Ra in general formula (I)) or -ORm (where Rm is an aliphatic group) , represents an aromatic group or a heterocyclic group). X1 and X2 represent an oxygen atom or a sulfur atom. )represent. General formula (III) [Formula 5] In the formula, R31, R32 and R33 are R of general formula (I)
It is synonymous with 11. R3a has the same meaning as R2a in general formula (II). W represents a divalent linking group. General formula (IV) embedded image In the formula, R41 and R42 have the same meaning as R11 in general formula (I). L2 represents a divalent linking group. Z represents a heterocyclic group. n represents 0 or 1. General Formula (V) embedded image In the formula, L3 represents a divalent linking group containing an aliphatic group, an aromatic group, a heterocyclic group, or a combination thereof. A represents a carboxyl group, a phosphono group, a sulfo group or a hydroxy group. R51, R52, R53, R54, R
55, R56 and R57 may be the same or different and each represents a hydrogen atom, an aliphatic group or a heterocyclic group. R58
and R59 may be the same or different and each hydrogen atom,
Represents an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfinyl group. Further, R58 and R59 may be connected to form a ring. t and u represent 0 or 1. [Claim 3] The color developing solution has the following general formula (Dev
3. The method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that it contains a p-phenylenediamine derivative represented by: General formula (Dev) [Image Omitted] In the formula, R1 and R3 are alkyl groups having 1 to 4 carbon atoms,
R2 is a 3-4 linear or branched alkylene group. 4. The silver halide photographic material according to claim 1 or 2, wherein the processing time of the photographic material is within 120 seconds from the beginning of the developing process to the end of the drying process. Processing method.