JPH0833643B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method of processing an exposed silver halide color photographic light-sensitive material (hereinafter referred to as color light-sensitive material) (hereinafter simply referred to as processing), and particularly, to a method of desilvering performance. It relates to an improved rapid processing method.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color development step and a desilvering step. In the color developing step, the exposed silver halide is reduced by the color developing agent to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. The silver formed here is oxidized by a bleaching agent in the subsequent desilvering step, further converted into a soluble silver complex by the action of a fixing agent, and dissolved and removed.

In addition to the above basic steps, the actual development processing includes various auxiliary steps for maintaining the photographic and physical qualities of the image, improving the storability of the image, and the like.
For example, a hardening bath, a stopping bath, an image stabilizing bath, a washing bath and the like.

In recent years, there has been a strong demand in the industry for speeding up the processing, that is, for shortening the time required for the processing, and in particular, shortening the desilvering process, which occupies almost half of the processing time, has become a serious problem.

Generally, bleaching agents such as red blood salts, dichromates, ferric chloride, ferric aminopolycarboxylic acid complex salts, and persulfates are known.

However, red blood salts and dichromates have pollution problems related to cyanide compounds and hexavalent chromium, and their use requires special treatment equipment. Also, for ferric chloride,
In the subsequent washing step with water, there are problems such as generation of iron hydroxide and generation of stains, which causes various obstacles in practical use. Persulfate has the disadvantage that it has a very weak bleaching action and requires a remarkably long bleaching time.

Aminopolycarboxylic acid ferric iron complex salts (especially ethylenediaminetetraacetic acid ferric iron complex salt) have few pollution problems,
Further, it is the most widely used bleaching agent at present because it has no problem in storage like persulfate. However, the bleaching power of the ferric aminopolycarboxylic acid complex is not always sufficient.

Conventionally, as a means for speeding up the desilvering process, a bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt and thiosulfate in one solution, which is described in German Patent 866,605, is known. ing. However, in this case,
Originally, a ferric aminopolycarboxylic acid complex salt having a weak oxidizing power (bleaching power) is allowed to coexist with a thiosulfate having a reducing power, so that the bleaching power is remarkably weakened, and a particularly high sensitivity and a high silver content color photographic light-sensitive material are used. There is a drawback in that it is extremely difficult to sufficiently desilver the material and it cannot be put to practical use.

On the other hand, as a method of increasing the bleaching power, a method of adding various bleaching accelerators to a bleaching bath, a bleach-fixing bath or a prebath thereof has been proposed. Such bleach accelerators include, for example, U.S. Patent No. 3,893,858, British Patent No. 1138842.
Specification, various mercapto compounds as described in JP-A-53-141623, compounds having a disulfide bond as described in JP-A-53-95630, JP-B-53-9854 Thiazolidine derivatives as described in JP-A-53-94927, Isothiourea derivatives as described in JP-A-53-94927, JP-B-45-8506 and JP-B-49-26
586, thiourea derivatives as described in JP-A-49-42349, thioamide compounds as described in JP-A-49-42349, dithiocarbamate salts as described in JP-A-55-26506, US Patent And arylene diamine compounds such as those described in the specification of No. 4552834.

Although some of these bleaching accelerators certainly show bleaching acceleration results, they are expensive and have insufficient stability in a bath having a bleaching ability, and therefore, they are not practical. I'm not satisfied with.

In contrast, Research Disclosure Item N
Nos. 24241 and 11449 and JP-A-61-20124 describe a bleaching accelerator compound-releasing coupler.

(Problems to be Solved by the Invention) However, such a bleach-accelerating compound-releasing coupler releases a bleach-accelerating compound having a mercapto group by a coupling reaction with an oxidant of a color-developing agent in the color-developing step, and the released compound is released. Since the bleach-accelerating compound is unstable in the presence of sulfite, when it is processed with a conventional color-developing solution containing sulfite, a sufficient bleach-accelerating effect can be obtained even by using such a bleach-accelerating compound-releasing coupler. It was found that the problem was not achieved.

Further, when the light-sensitive material containing the bleach-accelerating compound-releasing coupler is processed with a color developer containing a sulfite, the photographic performance obtained tends to be deteriorated.

Accordingly, the present invention is to provide a method for processing a silver halide color photographic light-sensitive material capable of achieving an improved bleach-accelerating effect by using the bleach-accelerating compound releasing coupler.

A further object of the present invention is to provide a method of processing a silver halide color photographic light-sensitive material capable of maintaining good photographic performance.

(Means for Solving the Problems) The above-mentioned problems of the present invention are obtained by subjecting a silver halide color photographic light-sensitive material to imagewise exposure, color development, and then processing with a processing solution having a bleaching ability. The photographic light-sensitive material contains a compound that releases a bleaching accelerator by reacting with an oxidized product of an aromatic primary amine type color developing agent (hereinafter referred to as a bleaching accelerator releasing compound), and contains sulfite ion and The concentration of bisulfite ion is 1 x 10 per developer.
It has been found to be solved by a processing method of a silver halide color photographic light-sensitive material characterized by being ^-2 mol or less (including 0).

That is, by substantially removing the sulfite ion-releasing compound in the color developer according to the present invention, the bleach-accelerating effect of the bleach-accelerating agent-releasing compound is remarkably improved.
Furthermore, it has been found that the photographic performance obtained is also improved.

The compound that releases the bleaching accelerator in the present invention is preferably a compound represented by the following general formula (I).

Formula (I) A- (L) _p -Z (In the formula, A represents a group in which the bond with (L) _p -Z is cleaved by the reaction with an oxidized product of the developing agent, and L represents a timing group or a developing agent. Represents a group in which the bond with Z is cleaved by the reaction with an oxidant, p represents an integer of 0 to 3, and when p is plural, p L's represent the same or different;
Z represents a group exhibiting a bleaching promoting action when the bond with A- (L) _p is cleaved. ) Further, compounds represented by the following general formula (I ′) are preferable.

General formula (I ') A- (L ₁ ) _a- (L _{2 b} Z (In the formula, A is (L ₁ ) _a- (L ₂ ) due to reaction with an oxidized product of a developing agent.
represents a group in which the bond with _b- Z is cleaved, L ₁ represents a timing group or a group in which the bond with (L ₂ ) _b -Z is cleaved by a reaction with an oxidized product of a developing agent, and L ₂ represents a timing group. Alternatively, it represents a group in which the bond with Z is cleaved by the reaction with an oxidized product of a developing agent, and Z represents a group having _a bleaching promoting action when the bond with A- (L ₁ ) _a- (L ₂ ) _b is cleaved. , A and b each represent 0 or 1. In the general formulas (I) and (I ′), A represents a coupler residue or a redox group.

Known coupler residues can be used as the coupler residue represented by A. For example, a yellow coupler residue (for example, an open-chain ketomethylene type coupler residue), a magenta coupler residue (for example, a 5-pyrazolone type, a pyrazoloimidazole type, a pyrazolotriazole type coupler residue, etc.), a cyan coupler residue (for example, a phenol type) , Naphthol-type coupler residues), and non-color-forming coupler residues (for example, indanone-type and acetonephenone-type coupler residues). Also, U.S. Pat.Nos. 4,315,070 and 4,183,75
It may be a heterocyclic coupler residue described in No. 2, No. 3,961,959 or No. 4,171,223.

In the general formula (I '), when A represents a coupler residue, preferred examples of A are the following general formulas (Cp-1) and (Cp-
2), (Cp-3), (Cp-4), (Cp-5), (Cp-
6), (Cp-7), (Cp-8), (Cp-9) or (Cp
-10) when it is a coupler residue. These couplers are preferred because of their high coupling speed.

General formula (Cp-1) General formula (Cp-2) General formula (Cp-8) General formula (Cp-9) General formula (Cp-10) The free bond derived from the coupling position in the above formula represents the bonding position of the coupling leaving group.

In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R
_{If 58} , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ or R ₆₃ contains a sparing resistant group, it is selected to have a total carbon number of 8 to 40, preferably 10 to 30, otherwise In this case, the total number of carbon atoms is preferably 15 or less. In the case of a bis-type, telomer-type or polymer-type coupler, any of the above substituents represents a divalent group and connects repeating units and the like. In this case, the range of uniprime numbers may be out of regulation.

Hereinafter, R _{51 to} R ₆₃ , d and e will be described in detail. In the following, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, R ₄₃ ,
R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ are each R
_{Has the} same meaning as ₄₂ . R ₅₄ has the same meaning as R ₄₁ , R ₄₁ S-group, R ₄₃ O-group, Alternatively, it represents an N≡C-group.

R ₅₅ represents a group having the same meaning as R ₄₁ . R ₅₆ and R ₅₇ are each
A group having the same meaning as R ₄₃ group, R ₄₁ S-group, R ₄₃ O-group, Represents R ₅₈ represents a group having the same meaning as R ₄₁ . R ₅₉ is R ₄₁
A group with the same meaning as R ₄₁ O- group, R ₄₁ S- group, halogen atom, or Represents d represents 0 to 3.

When d is plural, plural R _59's represent the same substituent or different substituents. Further, each R ₅₉ may be linked as a divalent group to form a cyclic structure. Examples of divalent groups for forming a cyclic structure are Is a typical example. Where f is 0 to 4
And g is an integer of 0 to 2, respectively. R ₆₀ is R
Represents a group having the same meaning as ₄₁ . R ₆₁ is a group having the same meaning as R ₄₁ ,
R ₆₂ represents a group having the same meaning as R _41, R ₄₁ CONH- group, a. R ₆₂
It is a group of the same meaning as R _41, R ₄₁ OCONH- group, R ₄₁ SO ₂ NH- group, R ₄₃ O- group, R ₄₁ S- group, halogen atom or Represents R ₆₃ has the same meaning as R ₄₁ , It represents an R ₄₁ SO ₂ — group, an R ₄₃ OCO— group, an R ₄₃ O—SO ₂ — group, a halogen atom, a nitro group, a cyano group or an R ₄₃ CO— group. e represents an integer of 0 to 4. When there are plural R ₆₂ or R _63, they represent the same or different.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
Representative examples include methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl,
(I) -butyl group, (t) -amino group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group,
Examples thereof include a 1,1,3,3-tetramethylbutyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group.

The aromatic group is a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted naphthyl group.

The heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably selected from nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and preferably having 3 to 8 members. Is. Typical examples of the heterocyclic group are 2-pyridyl group, 2-thienyl group, 2-furyl group,
1-imidazolyl group, 1-indolyl group, phthalimido group, 1,3,4-thiadiazol-2-yl group, 2-quinolyl group, 2,4-dioxo-1,3-imidazolidin-5-yl group, 2 Examples include a 4,4-dioxo-1,3-imidazolidin-3-yl group, a succinimide group, a 1,2,4-triazol-2-yl group and a 1-pyrazolyl group.

Representative substituents when the aliphatic hydrocarbon group, the aromatic group and the heterocyclic group have a substituent, a halogen atom, R ₄₇ O- group, R ₄₆ S- group, R ₄₆ SO ₂ -group, R ₄₇ OCO-group, A group having the same meaning as R ₄₆ , R ₄₆ COO − group, R ₄₇ OSO ₂ — group, cyano group or nitro group can be mentioned. Here, R ₄₆ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₄₇ , R _48, and R ₄₉ each represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. The meaning of an aliphatic group, an aromatic group or a heterocyclic group has the same meaning as previously defined.

Next, preferred ranges of R _{51 to} R ₆₃ , d and e will be described.

R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ , R ₅₃
And R ₅₅ is preferably an aromatic group. R ₅₄ is R ₄₁ CONH- group,
Or Is preferred. R ₅₆ and R ₅₇ are preferably an aliphatic group, R ₄₁ O— group, or R ₄₁ S— group. R ₅₈ is preferably an aliphatic group or an aromatic group. In formula (Cp-6), R ₅₉ is preferably a chlor atom, an aliphatic group or an R ₄₁ CONH-group. d is 1
Or 2 is preferable. R ₆₀ is preferably an aromatic group. In formula (Cp-7), R ₅₉ is preferably R ₄₁ CONH-group. In the general formula (Cp-7), d is preferably 1. R ₆₁ is preferably an aliphatic group or an aromatic group. In the general formula (Cp-8), e is preferably 0 or 1. R ₄₁ for R ₆₂ OCON
The H-group, the R ₄₁ CONH-group or the R ₄₁ SO ₂ NH-group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. In the general formula (Cp-9), R ₆₃ is R ₄₁ CONH-group, R ₄₁ SO ₂ NH
-Base, A nitro group or a cyano group is preferred.

In the general formula (Cp-10), R ₆₃ is R ₄₃ CCO- group or R ₄₃ CO- group.

Next, typical examples of R _{51 to} R ₆₃ will be described. Examples of R ₅₁ include (t) -butyl group, 4-methoxyphenyl group, phenyl group, 3- {2 (2,4-di-t-amylphenoxy) butanamide} phenyl group, and methyl group. R ₅₂ and R ₅₃ are 2-chloro-5-dodecyloxycarbonylphenyl group, 2-chloro-5-hexadecylsulfonamidophenyl group, 2-chloro-5-
Tetradecanamidophenyl group, 2-chloro-5- {4
-(2,4-Di-t-amylphenoxy) butanamide}
Phenyl group, 2-chloro-5- {2- (2,4-di-t-
Amylphenoxy) butanamide} phenyl group, 2-methoxyphenyl group, 2-methoxy-5-tetradecyloxycarbonylphenyl group, 2-chloro-5- (1-ethoxycarbonylethoxycarbonyl) phenyl group, 2-
Pyridyl group, 2-chloro-5-octyloxycarbonylphenyl group, 2,4-dichlorophenyl group, 2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl group, 2-chlorophenyl group or 2-ethoxyphenyl group Is mentioned.

R ₅₄ is 3- {2- (2,4-di-t-amylphenoxy) -butanamide} benzamide group, 3- {4-
(2,4-di-t-amylphenoxy) butanamide} benzamide group, 2-chloro-5-tetradecanamideaniline group, 5- (2,4-di-t-amylphenoxyacetamide) benzamide group, 2-chloro- 5-dodecenylsuccinimidoanilino group, 2-chloro-5- {2-
(3-t-butyl-4-hydroxyphenoxy) tetradecanamide} anilino group, 2,2-dimethylpropanamide group, 2- (3-pentadecylphenoxy) butanamide group, pyrrolidino group or N, N-dibutylamino group Can be mentioned. As R ₅₅ , 2,4,6-trichlorophenyl group, 2-chlorophenyl group, 2,5-dichlorophenyl group, 2,3-dichlorophenyl group, 2,6-dichloro-4-methoxyphenyl group, 4- {2 A-(2,4-di-t-amylphenoxy) butanamide} phenyl group or a 2,6-dichloro-4-methanesulfonylphenyl group is a preferred example. R ₅₆ is a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group, or 3- (2,4
-Di-t-amylphenoxy) propyl group. As R ₅₇ , 3- (2,4-di-t-amylphenoxy) propyl group, 3- [4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] tetradecanamido} phenyl] propyl group, methoxy Group, methylthio group, ethylthio group, methyl group, 1-methyl-2- (2-
Octyloxy-5- [2-octyloxy-5- (1,
1,3,3-Tetramethylbutyl) phenylsulfonamide] phenylsulfonamide] ethyl group, 3- {4-
(4-dodecyloxyphenylsulfonamido) phenyl} propyl group, 1,1-dimethyl-2- (2-octyloxy-5- (1,1,3,3-tetramethylbutyl) phenylsulfonamido] ethyl group, Or a dodecylthio group, R ₅₈ is 2-chlorophenyl group, pentafluorophenyl group, heptafluoropropyl group, 1
-(2,4-di-t-amylphenoxy) propyl group, 3
-(2,4-di-t-amylphenoxy) propyl group, 2,4
A di-t-amylmethyl group or a furyl group may be mentioned. R ₅₉ is a chloro atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a 2- (2,4-di-t-amylphenoxy) butanamide group, a 2- (2,4
-Di-t-amylphenoxy) hexanamide group, 2-
(2,4-di-t-octylphenoxy) octanamide group, 2- (2-chlorophenoxy) tetradecanamide group, 2- {4- (4-hydroxyphenylsulfonyl)
Phenoxy} tetradecanamide group, or 2- {2-
(2,4-di-t-amylphenoxyacetamido) phenoxy} butanamide group. 4 for R ₆₀
-Cyanophenyl group, 2-cyanophenyl group, 4-butylsulfonylphenyl group, 4-propylsulfonylphenyl group, 4-chloro-3-cyanophenyl group, 4-ethoxycarbonylphenyl group, or 3,4-dichlorophenyl group Can be mentioned. R ₆₁ is dodecyl group, hexadecyl group, cyclohexyl group, 3- (2,4-di-t-amylphenoxy) propyl group, 4- (2,4-di-t-amylphenoxy) butyl group, 3-dodecyl group. Examples thereof include an oxypropyl group, a t-butyl group, a 2-methoxy-5-dodecyloxycarbonylphenyl group, and a 1-naphthyl group. Examples of R ₆₂ include an isobutyloxycarbonylamide group, an ethoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfonamide group, a benzamide group, a trifluoroacetamide group, a 3-phenylureido group, a butoxycarbonylamino group, or an acetamide group. . R ₆₃ is 2,4-di-t-amylphenoxyacetamide group, 2- (2,4-di-t-amylphenoxy) butanamide group, hexadecylsulfonamide group, N-methyl-N-octadecylsulfur group. Faamoyl group, N, N-dioctylsulfamoyl group, 4-t-octylbenzoyl group, dodecyloxycarbonyl group, chlor atom, nitro group, cyano group, N- {4- (2,4-
A di-t-amylphenoxy) butyl} carbamoyl group,
Examples thereof include N-3- (2,4-di-t-amylphenoxy) propylsulfamoyl group, methanesulfonyl group and hexadecylsulfonyl group.

When A represents a redox group in the general formula (I),
Specifically, it is represented by the following general formula (II).

In formula (II) A ₁ -P- (X = Y) _n -QA ₂ , in which P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and n and X At least one represents a methine group having-(L ₁ ) _a- (L ₂ ) _b -Z as a substituent, other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n is 1 To 3 (n X's and n Y's are the same or different), and A ₁ and A ₂ are each a hydrogen atom or a group removable by an alkali. Where either P, X, Y, Q, A ₁ or A ₂ is 2
The case where one substituent is a divalent group and connected to form a cyclic structure is also included. For example, (X = Y) _n is a benzene ring,
This is the case where a pyridine ring or the like is formed.

When P and Q represent a substituted or unsubstituted imino group, preferably an imino group substituted with a sulfonyl group or an acyl group, P and Q are represented as follows.

Here, the * mark represents the position at which it binds to A ₁ or A _2, and *
The asterisk (*) represents the position of bonding to one of the free bonds of (X = Y _n ).

In the formula, the group represented by G is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32 carbon atoms, preferably 1 to 22 (eg, methyl group, ethyl group). Group, benzyl group, phenoxybutyl group, isopropyl group, etc.), a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (eg, phenyl group, 4-methylphenyl group,
1-naphthyl group, 4-dodecyloxyphenyl group and the like), or a 4- to 7-membered heterocyclic group selected from nitrogen atom, sulfur atom or oxygen atom as a hetero atom (for example, 2-pyridyl group, 1-phenyl- 4-imidazolyl group, 2-furyl group,
A benzocenyl group) is a preferred example.

In the general formula (II), P and Q are preferably each independently an oxygen atom or a group represented by the general formula (N-1).

A group in which A ₁ and A ₂ can be removed by an alkali (hereinafter,
When referred to as a precursor group), it is preferably a hydrolyzable group such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group and a sulfonyl group, a type utilizing the reverse Michael reaction described in US Pat. No. 4,009,029. Precursor group of U.S. Pat. No. 4,31
Precursor group of the type utilizing an anion generated after the ring opening reaction described in 0,612 as an intramolecular nucleophilic group, U.S. Pat.Nos. 3,674,478, 3,932,480 or 3,993,661.
A precursor group in which the anion described in US Pat.
Precursor groups described in 4,335,200 which cause a cleavage reaction by electron transfer of anions reacted after ring cleavage or precursor groups using an imidomethyl group described in US Pat. Nos. 4,363,865 and 4,410,618 are mentioned.

In the general formula (II), P is preferably an oxygen atom and A ₂ is a hydrogen atom.

More preferably in the general formula (II), X and Y
But as a substituent _{- (L 1) a (L} 1) b except when -Z is a methine group having other X and Y is when a substituted or unsubstituted methine group.

Among the groups represented by the general formula (II), particularly preferable groups are represented by the following general formula (III) or (IV).

General formula (III) General formula (IV) In the formula, * marks represent the bonding position of-(L ₁ ) _a- (L ₂ ) _b -Z, and P, Q, A ₁ and A ₂ have the same meanings as described in the general formula (II). R ₆₄ represents a substituent, and q represents an integer of 0, 1 or 3. When q is 2 or more, two or more R ₆₄ may be the same or different, and two R ₆₄
2 each when ₆₄ is a substituent on an adjacent carbon
It also includes a case in which a cyclic structure is formed by connecting as a valent group.
In that case, it becomes a benzene condensed ring, for example, naphthalenes,
Benzonorhornenes, chromanes, indoles, benzothiophenes, quinolines, benzofurans, 2,3
-A ring structure such as dihydrobenzofurans, indans or indenes, which may further have one or more substituents; Examples of preferred substituents when having substituents on these condensed rings and preferred examples of R ₆₄ when R ₆₄ does not form a condensed ring are those listed below. That is, R ₄₁ group, halogen atom, R ₄₃ O-- group, R
₄₃ S-group, R ₄₃ OOC-group, R ₄₁ SO ₂ -group, Cyano group, or Is mentioned.

Here, R ₄₁ , R ₄₃ , R ₄₄ and R ₄₅ have the same meaning as described above. The following are typical examples of R ₆₄ . That is, methyl group, ethyl group, t-butyl group, methoxy group, methylthio group, dodecylthio group, 3-
(2,4-di-t-amylphenoxy) propylthio group,
N-3- (2,4-di-t-amylphenoxy) propylcarbamoyl group, N-methyl-N-octadecyloxycarbamoyl group, methoxycarbonyl group, dodecyloxycarbonyl group, propylcarbamoyl group, hydroxyl group or N, N A dioctylcarbamoyl group. An example of two R ₆₄ forming a ring structure is And a group represented by.

In the general formulas (III) and (IV), P and Q preferably represent an oxygen atom.

In formulas (III) and (IV), A ₁ and A ₂ preferably represent hydrogen atoms.

The groups represented by L ₁ and L ₂ in the general formula (I ′) may or may not be used in the present invention. It is preferable not to use it, but it is appropriately selected according to the purpose. L ₁ and L ₂
When represents a timing group, the following known linking groups and the like can be mentioned.

(1) Group utilizing cleavage reaction of hemiacetal, for example, US Pat. No. 4,146,396, JP-A-60-249148 and JP-A-60-249148.
No. 249149, and is a group represented by the following general formula. Here, the * mark represents the position bonded to the left side in the general formula (II), and the ** mark represents the position bonded to the right side in the general formula (II).

In the formula, W is an oxygen atom, a sulfur atom or Represents a group, R ₆₅ and R ₆₆ represent a hydrogen atom or a substituent, R ₆₇ represents a substituent, and t represents 1 or 2. When t is 2, two Represents the same or different. R ₆₅ and R ₆₆
When R represents a substituent and typical examples of R ₆₇ are respectively R ₆₉
Group, R ₆₉ CO- group, R ₆₉ SO ₂ -group, Is mentioned. Here, R ₆₉ has the same meaning as R ₄₁ described above, and R ₇₀ has the same meaning as R ₄₃ . R ₆₅ , R ₆₆
And R ₆₇ each represent a divalent group, and include the case where they are linked to form a cyclic structure. Specific examples of the group represented by formula (T-1) include the following groups.

(2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,962 can be mentioned. It can be represented by the following general formula.

General formula (T-2) * -Nu-Link-E-** In the formula, * mark represents the position bonded to the left side in the general formula (II), and ** mark bonded to the right side in the general formula (II). Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and a bond with ** is cleaved by a nucleophilic attack from Nu. Link is a group capable of forming, and Link represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) are as follows.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, it is a group represented by the following general formula described in U.S. Pat. No. 4,409,323 or 4,421,845.

General formula (T-3) In the formula, *, **, W, R ₆₅ , R ₆₆ and t are (T-
It has the same meaning as described in 1). Specific examples include the following groups.

(4) A group that utilizes a cleavage reaction due to hydrolysis of an ester.

For example, the following groups are the connecting groups described in West German Published Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1).

(5) Group Utilizing Iminoketal Cleavage Reaction For example, a linking group described in US Pat. No. 4,546,073, which is a group represented by the following general formula.

General formula (T-6) In the formula, * mark, ** mark and W have the same meaning as described in formula (T-1), and R ₆₈ has the same meaning as R ₆₇ . Specific examples of the group represented by formula (T-6) include the following groups.

When the group represented by L ₁ in the general formula (I ′) represents a group that cleaves from A and then reacts with an oxidized product of a developing agent to cleave (L ₂ ) _b -Z, specifically, after cleaving from A, A group that serves as a coupler or a group that serves as a redox group. Similarly, L ₂
The group represented by represents a group which is cleaved from A- (L ₁ ) _b and then cleaves Z by reacting with an oxidized product of a developing agent.
It is a group that becomes a coupler or a redox group after being cleaved from (L ₁ ) _b .

In the case of a phenol type coupler, for example, a group serving as a coupler is a group bonded to A- or A- (L ₁ ) _b-at an oxygen atom except a hydrogen atom of a hydroxyl group.
Further, in the case of a 5-pyrazolone type coupler, A- or A- (L ₁ ) _{b at} an oxygen atom obtained by removing a hydrogen atom from a hydroxyl group of a type tautomerized to 5-hydroxypyrazole
-Is associated with. In these examples, a phenol-type coupler or a 5-pyrazolone-type coupler is obtained only after the compound is separated from A- or A- (L ₁ ) _b- . They have (L ₂ ) _b -Z or Z at their coupling position.

When L ₁ and L ₂ represent a group which serves as a coupler, it is preferably represented by the following general formula (V), (VI), (VII) or (VII
It is a group represented by I). In the formulas below, the * mark represents the position bonded to the left side in the general formula (I), and the ** mark represents the position bonded to the right side.

In the formula, V ₁ and V ₂ represent a substituent, V ₃ , V ₄ , V ₅ and V ₆ represent a nitrogen atom or a substituted or unsubstituted methine group, V ₇ represents a substituent, and x represents 0 to an integer of 4, x is a plurality of time V ₇ represent the same or different, two V ₇ may combine with each other to form a ring structure linked. V ₈ represents -CO- group, -SO ₂ - represents a group, an oxygen atom or a substituted imino group, V ₉ is And represents a non-metal atom group for forming a 5- to 8-membered ring, and V ₁₀ represents a hydrogen atom or a substituent. However, V ₁ and V ₂ each represent a divalent group, and when joined together form a 5- or 8-membered ring. May be.

V ₁ preferably represents an R ₇₁ group, V ₂ is an R ₇₂ group, R ₇₂ CO-
Base, R ₇₂ SO ₂ - group, R ₇₂ S- group, R ₇₂ O-group, or, Is a preferred example. Examples of the case where V ₁ and V ₂ are linked to each other to form a ring include an indene ring, indoles, pyrazoles, and benzothiophenes.

V ^3, V _4, V ₅ or V ₆ is R ₇₁ group substituent is preferably when represents a substituted methine group,, R ₇₃ O-group, R ₇₁ S- group, or include R ₇₁ CONH- group.

Preferred examples of V ₇ include halogen atom, R ₇₁ group, R ₇₁ CO
NH- group, R ₇₁ SO ₂ NH- group, R ₇₃ O- group, R ₇₁ S- group, R ₇₁ CO— or R ₇₃ OOC groups are preferred examples. Examples of the case where a plurality of V ₇ are linked to each other to form a cyclic structure include naphthalene, quinoline, oxindole and benzodiazepine-2,4.
-Diones, benzimidazol-2-ones or benzothiophenes.

When V ₈ represents a substituted imino group, it is preferably R ₇₃ N group.

V ₉ is Preferred ring structures composed of are indoles, imidazolinones, 1,2,5-thiadiazoline-1,1-dioxides,
3-pyrazolin-5-ones, 3-isoxazoline-
5-ones, or The kind is mentioned.

Preferred examples of V ₁₀ are R ₇₃ group, R ₇₃ O-group, Alternatively, it is a R ₇₁ S— group.

In the above, R ₇₁ and R ₇₂ represent an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₃ , R ₇₄ and R ₇₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Here, the aliphatic group, aromatic group and heterocyclic group have the same meanings as described above for R ₄₁ . However, the total number of carbon atoms contained in these groups is preferably 10 or less.

Typical examples of the group represented by the general formula (V) include the following groups.

Typical examples of the group represented by the general formula (VI) include the following groups.

Typical examples of the group represented by the general formula (VII) include the following groups.

Typical examples of the group represented by the general formula (VIII) include the following groups.

When the groups represented by L ₁ ) and L ₂ ) in the general formula (I ′) represent a group which serves as a redox group, it is preferably a group represented by the following general formula (IX).

Formula (IX) * -P '- ( X' = Y ') n'-Q'-A' ₂ where symbol * represents the general formula (I) the position at which the group bonds to the left, A' _2, P ′, Q ′ and n ′ are represented by the general formula (I
A _{2 has} the same meaning as A ₂ , P, Q and n described in I), and at least one of n ′ X ′ and n ′ Y ′ is L ₂ Z or a methine group having Z as a substituent. And other X'and Y'represent a substituted or unsubstituted methine group or a nitrogen atom. Wherein _{A '2, P', Q} ', X' also encompasses the case where any two of the substituents and Y 'to form a cyclic structure a divalent group. Such a ring structure is, for example, a benzene ring or a pyridine ring.

In the general formula (IX), P'preferably represents an oxygen atom and Q'preferably represents an oxygen atom or the following. Here mark * 'represents a bond that binds to, the mark ** A' (X '= Y' ) n represents a bond that binds to _2.

In the formula, G'has the same meaning as G described in the general formulas (N-1) and (N-2).

Q'is particularly preferably an oxygen atom or Is a group represented by.

Particularly preferable groups in the group represented by the general formula (IX) are those represented by the following general formula (X) or (XI).

General formula (X) General formula (XI) In the formula, the * mark represents the position bonded to the left side of L ₁ or L ₂ in the general formula (I), and the ** mark represents the position bonded to the right side. R ₇₆ has the same meaning as R ₆₄ described in formula (III) or (IV). y represents 0 to 3, and when y is plural, R ₇₆ represents the same or different. Also included is the case where two R _76's are linked to form a cyclic structure.

Particularly preferred examples of R ₇₆ include the following groups. That is, an alkoxy group (eg, methoxy group, ethoxy group, etc.), an acylamino group (eg, acetamide group, benzamide group, etc.), a sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), an alkylthio group (eg, methylthio group, Ethylthio group, carbamoyl group (for example, N-propylcarbamoyl group, Nt-butylcarbamoyl group, Ni-)
Propylcarbamoyl group, etc.), alkoxycarbonyl group (eg methoxycarbonyl group, propoxycarbonyl group etc.), aliphatic (eg methyl group, t-butyl group etc.), halogen atom (eg fluoro group, chloro group etc.), suphamoyl group ( For example, N-propylsulfamoyl group, sulfamoyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), hydroxyl group, or carboxy group. A typical example of the case where two R ₇₆ are linked to form a ring structure is (The asterisk and asterisk have the same meanings as described in the general formula (XI)).

The group represented by Z in the general formula (I ′) is specifically a known bleaching accelerator residue. US Patent No.
3,893,858, British Patent No. 1138842, various mercapto compounds as described in JP-A-53-141623, having a disulfide bond as described in JP-A-53-95630. Compounds, thiazolidine derivatives as described in JP-B-53-9854, JP
Isothiourea derivatives as described in JP-A-53-94927, JP-B-45-8506, and thiourea derivatives as described in JP-B-49-26586, described in JP-A-49-42349 Thioamide compound as described in JP-A-55-2
Examples thereof include dithiocarbamate salts described in 6506, and arylene diamine compounds described in US Pat. No. 4,552,834. These compounds have a substitutable heteroatom contained in the molecule,
General formula (I ') A- in _{(L 1) a - (L} 2) b - as preferred examples for binding.

The group represented by Z is more preferably the following general formula (XI
A group represented by I), (XIII) or (XV).

General formula (XII) General formula (XIII) General formula (XIV) In the formula, * indicates a position to be bonded to A- (L ₁ ) _a- (L ₂ ) _b- , R ₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and R ₂ represents a group having the same meaning as R ₁ , a divalent aromatic group having 6 to 10 carbon atoms or a 3- to 8-membered, preferably 5- or 6-membered, divalent heterocyclic group, and X ₁ represents -0 -, - S -, - COO -, - SO 2 -, X ₂ represents an aromatic group having 6 to 10 carbon atoms, X ₃ represents a 3- to 8-membered ring having at least one carbon atom bonded to S in the ring, preferably 5-membered or 6-membered. Represents a heterocyclic group of a member ring, Y ₁ is a carboxyl group or a salt thereof,
Sulfo group or salt thereof, hydroxyl group, phosphonic acid group or salt thereof, hydroxyl group, phosphonic acid group or salt thereof, amino group (may be substituted with an aliphatic group having 1 to 4 carbon atoms), -NHSO _2- R ₅ or —SO ₂ NH—R ₅ group (here, salt means sodium salt, potassium salt, ammonium salt, etc.), and Y ₂ is a group or hydrogen atom having the same meaning as described for Y _1. , R represents 0 or 1, l represents an integer of 0 to 4, and m represents 1
Represents an integer of 4 to 4, and u represents an integer of 0 to 4. However, m Y ₁ is At each substitutable position, when m is plural, m Y _1's represent the same or different, and when l is plural, l (X ₁ ) _r -R ₂ are the same or Represents different things. Here, R ₃ , R ₄ and R ₅ each represent a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.
When R ₁ to R ₅ represent an aliphatic group, a chain or a ring,
It may be linear or branched, saturated or unsaturated, substituted or unsubstituted. Substitution is preferred,
Examples of the substituent include a halogen atom, an alkoxy group (eg, methoxy group, ethoxy group), an alkylthio group (eg, methylthio group, ethylthio group) and the like.

The aromatic group represented by X ₂ and the aromatic group when R ₂ represents an aromatic group may have a substituent. For example, those exemplified as the aforementioned aliphatic group substituents can be mentioned.

When the heterocyclic group represented by X ₃ and R ₂ represents a heterocyclic group, the heterocyclic group is a saturated or unsaturated, substituted or unsubstituted heterocyclic group having an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom. is there. For example, a pyridine ring,
Examples thereof include an imidazole ring, a piperidine ring, an oxirane ring, a sulfolane ring, an imidazolidine ring, a thiazepine ring and a pyrazole ring. Examples of the substituent include those listed above as the aliphatic group substituent.

Specific examples of the group represented by the general formula (XII) include the followings.

−SCH ₂ CH ₂ CO ₂ H, −SCH ₂ CO ₂ H, −SCH ₂ CONHCH ₂ CO ₂ H, −SCH ₂ CH ₂ OCH ₂ CO ₂ H, −SCH ₂ COOCH ₂ CH ₂ OH, −SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OH, −SCH ₂ CH ₂ SCH ₂ CO ₂ H, −SCH ₂ CH ₂ CH ₂ CO ₂ H, Specific examples of the group represented by the general formula (XIII) include the following.

Specific examples of the group represented by the general formula (XIV) include the followings.

The compound represented by the general formula (I ') of the present invention includes a case where the compound is a bis-form, a telomer or a polymer.
For example, in the case of a polymer, a polymer derived from a monomer represented by the following general formula (XV) and having a repeating unit represented by the general formula (XVI), or an oxide of an aromatic primary amine developing agent and a cup It is a copolymer with one or more products of a non-color-forming monomer containing at least one ethylene group having no ringing ability. Here, two or more kinds of the monomers represented by the general formula (XV) may be polymerized at the same time.

General formula (XV) General formula (XVI) In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and A ₁₁ represents -CONH-, -NHCONH-, -NHCOO-, -COO-, -SO.
_{2 -, - CO -, -} NHCO -, - SO 2 NH -, - NHSO 2 -, - OCO
Represents-, -OCONH-, -NH- or -O-, and A ₁₂ represents -CO
A represents NH- or -COO-, A ₁₃ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group, and the alkylene group may be linear or branched. (Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, examples of the aralkylene group include benzylidene, and examples of the arylene group include phenylene and naphthylene).

QQ represents a compound residue represented by the general formula (I ′), and may be bonded at any position except the group represented by Z of the substituents already described for these.

i, j, and k represent 0 or 1, but i, j,
And k cannot be 0 at the same time.

Here, the substituent of the alkylene group, aralkylene group or arylene group represented by A ₁₃ is an aryl group (for example, a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (for example, a methoxy group), an aryloxy group. (Eg phenoxy group), acyloxy group (eg acetoxy group), acylamino group (eg acetylamino group), sulfonamide group (eg methanesulfonamide group), sulfamoyl group (eg methylsulfamoyl group), halogen atom (eg fluorine , Chlorine, bromine, etc.), a carboxy group, a carbamoyl group (eg, methylcarbamoyl group), an alkoxycarbonyl group (eg, methoxycarbonyl group), and a sulfonyl group (eg, methylsulfonyl group). When there are two or more substituents, they may be the same or different.

Next, acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid and these acrylic acids are used as the non-color forming ethylene-like monomer that is not coupled with the oxidation product of the aromatic primary amine developing agent. Derived ester or amide, methylenebisacrylamide, vinyl ester, acrylonitrile, aromatic vinyl compound,
Examples include maleic acid derivatives and vinyl pyridines. The non-color-forming ethylenically unsaturated monomers used here may be used in combination of two or more.

The present invention also includes the case where any two groups represented by A, L ₁ , L ₂ and Z in the general formula (I ′) have a bond in addition to the bond represented by the general formula (I ′). . This second
The effect of the present invention can be obtained even if the bond is not cut during development. Examples of such bonds are, for example:

Among the above, as a particularly preferable example, the following general formula (XVI
It is represented by I).

General formula (XVII) Wherein L ₂ , b, Z, R ₅₈ and R ₅₉ have the same meanings as previously described, h and v each represent 0 or 1.
A ₁₄ represents a divalent organic residue forming a 5-membered to 8-membered ring.

As A ₁₄ , for example, -O-CH, And -S-CH group and the like.

Next, specific examples of the compound that releases the bleaching accelerator used in the present invention will be given, but the present invention is not limited thereto.

Others, research. Disclosure Item No. 24241
No. 11449, JP-A No. 61-201247, and Japanese Patent Application No. 61-252.
The compounds described in Nos. 847, 61-268870 and 61-268871 are also used in the same manner.

Further, the bleaching accelerator releasing compound used in the present invention is
It can be easily synthesized based on the description in the above patent specifications.

The amount of the bleaching accelerator releasing compound according to the present invention added to the light-sensitive material is 1 × 10 ⁷ mol to 1 × 10 ⁷ mol / m ² of the light-sensitive material.
^-1 mol is preferable, and 1 x 10 ^-6 mol to 5 x 10 ^-2 mol is particularly preferable. The bleach accelerator releasing compound according to the present invention is
It can be added to all layers of the light-sensitive material, but it is preferably added to the light-sensitive emulsion layer, and the effect becomes remarkable when it is added to more light-sensitive emulsion layers.

The color developer used for the development processing of the light-sensitive material of the present invention,
It is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3
-Methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-trienesulfone hydrochloride, tetraphenylborate, p- (t -Octyl) benzene sulfonate and the like. Salts of these diamines are generally more stable than those in the free state, and are preferably used.
Examples of aminophenol derivatives include o-aminophenol, p-aminophenol, 4-amino-2-
Methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene and the like are included.

In addition, LFA Messon's "Photographic Processing Chemistry", Focal Press (1966
(LFAMason, “Photographic Processing Chemis
try ", Focal Press) 226-229, U.S. Pat. No. 2,193,01
Nos. 5, 2,592,364 and JP-A-48-64933 may be used. If desired, two or more color developing agents may be used in combination.

In the present invention, the concentration of sulfite ion and bisulfite ion in the color developing solution is 1 × 10 ^-2 mol or less per developer or the concentration of the compound releasing these ions (sulfite ion releasing compound) is per developer. It is 1 × 10 ⁻² mol or less, and more preferably 0.8 × 10 ⁻² mol or less.

The term “sulfite ion-releasing compound” as used in the present invention refers to a compound that dissolves in water and generates (releases) sulfite ion or bisulfite ion in the solution, and examples thereof include alkali metal salts of sulfite and bisulfite or alkaline earth. Examples thereof include bisulfite addition products of metal salts, ketones or aldehydes.

Color developers include pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or antifoggants. Preservatives such as hydroxylamine, triethanolamine, compounds described in West German Patent Application (OLS) 2622950;
Organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates, 3,6-thiaoctane-
Development accelerators such as 1,8-diols; Dye-forming couplers; Competitive couplers; Nucleating agents such as sodium boron hydride; Auxiliary developing agents such as 1-phenyl-3-pyrazolidone; Viscosity enhancers; Ethylenediaminetetraacetic acid, Nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids represented by the compounds described in JP-A-58-195845. Acid, 1-hydroxyethylidene-1,1′-diphosphonic acid, organic phosphonic acid described in Research Disclosure 18170 (May 1979), aminotris (methylenephosphonic acid) ethylenediamine-N,
An aminophosphonic acid such as N, N ', N'-tetramethylenephosphonic acid, and a chelating agent such as phosphonocarboxylic acid described in Research Disclosure 18170 (May 1979) can be contained.

Color developing agent is about 0 per 1 general color developing solution.
It is used at a concentration of 1 g to about 30 g, more preferably about 1 g to about 15 g per color developing solution. In addition, p of color developing solution
H is usually greater than or equal to 7 and is most commonly used from about 9 to about 13.

In the present invention, when it is necessary to further improve the preservability of the color developing solution, a method of reducing the gas-liquid interface (for example, a floating pig), a method of using an organic preservative, or the like can be used.

Here, as the organic preservative, the following general formulas (A) to (D) are used.
It is preferable to include at least one compound of the above compounds in the color developing solution in order to achieve a better bleaching acceleration effect and to enhance the stability of the color developing solution.

General formula (A) In the formula, R ₁₀₁ and R ₁₀₂ represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₀₃ represents a substituted or unsubstituted alkylene group. The total carbon number of R ₁₀₁ , R ₁₀₂ and R ₁₀₃ is 3 or more.

General formula (B) In the formula, X ₁₁ represents a trivalent atom group necessary for completing the condensed ring. m ₁ represents an integer of 0 to 4, and n ₁ represents an integer of 1 to 5.

General formula (C) In the formula, R ₁₀₄ , R ₁₀₅ and R ₁₀₆ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ₁₀₄ and R ₁₀₅ ,
R ₁₀₄ and R ₁₀₆ or R ₁₀₅ and R ₁₀₆ may combine with each other to form a nitrogen-containing heterocycle.

General formula (D) In the formula, R ₁₀₇ , R ₁₀₈ , R ₁₀₉ and R ₁₁₀ each independently represent a hydrogen atom or an alkyl group, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ each independently represent an unsubstituted alkylene group, and X ₁₂ and X
₁₃ are independent -O -, - S -, - CO -, - SO 2 -, - SO- or represents a linking group composed of a combination of these linking groups (R ₁₁₄
Represents a hydrogen atom or an alkyl group), m ₂ and n ₂ represent 0, 1, 2 or 3, respectively.

 The general formula (A) will be described in more detail below.

General formula (A) In the formula, R ₁₀₁ and R _{102 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a hydroxyethyl group, a carboxymethyl group, N, N-diethylamino). R ₁₀₃ represents an ethyl group, a methoxypropyl group, a mesylethyl group, a butyl group, an isobutyl group, etc., and R ₁₀₃ is a substituted or unsubstituted alkylene group (preferably a group having 1 to 10 carbon atoms. For example, a methylene group, an ethylene group, a propylene group. , 2-hydroxypropylene group, etc.)
Represents The total carbon number of R ₁₀₁ , R ₁₀₂ and R ₁₀₃ is 3 or more.

In the general formula (A), R ₁₀₁ and R ₁₀₂ are preferably a hydrogen atom, an unsubstituted alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, or a carboxyalkyl group, and at least one of R ₁₀₁ and R ₁₀₂ More preferably, one is a hydrogen atom, an unsubstituted alkyl group or a hydroxylalkyl group.

In the general formula (A), R ₁₀₃ is preferably an unsubstituted alkylene group and a group having a carboxyl group, an amino group or a hydroxyl group as a substituent.

The number of carboxyl groups contained in the compound of the general formula (A) is preferably 3 or less, more preferably 2 or less.

The amount of the compound of the general formula (A) added is 0.01 to 50 g, preferably 0.1 to 20 g, per color developer.

Specific examples of the compound represented by formula (A) according to the present invention are shown below, but the present invention is not limited thereto.

A- (1) (HOC ₂ H _{4 2} N-CH ₂ COOH A- (2) HNCH ₂ COOH) ₂ A- (3) CH ₃ NCH ₂ COOH) ₂ A- (6) HOC ₂ H ₄ -NCH ₂ COOH) ₂ A- (7) (HOC ₂ H _{4 2} N- (CH _{2 2} NCH ₂ COOH) ₂ A- (8) (CH ₃ OC ₂ H ₄ ). ₂ NCH _{2 3} COOH A- (10) (HOC ₂ H ₄ OC ₂ H _{4 2} NCH _{2 3} COOH A- (12) HOC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ -NC ₂ H ₄ COOH) ₂ A- (14) CH ₃ SO ₂ C ₂ H ₄ NCH ₂ COOH) ₂ A- (17) NH ₂ CH _{2 3} COOH A- (18) CH ₃ NHC ₂ H ₄ COOH A- (19) (CH _{3 2} N-CH ₂ COOH Next, the compound represented by formula (B) will be described.

In the general formula (B), X ₁₁ preferably has 1 to 20 carbon atoms, more preferably 10 or less, and further preferably 6 or less.

In the general formula (B), m ₁ is preferably 3 or less,
It is preferable that n ₁ is 4 or less.

The compound of the general formula (B) may form a bis body, a tris body or the like with X ₁₁ .

Specific examples of X _{11 in} the general formula (B) include CH = N−, —CH ₂ CH ₂ N, And so on.

Next, among the general formulas (B), preferred are the compounds represented by the general formulas (Ba) and (Bb).

Where Y ₁₁ is Represents

R _{115 to} R ₁₁₇ represent a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a hydroxy group, a hydroxy group, an alkoxy group, etc., and a carbonyl group in combination with a carbon atom bonded to R ₁₁₆ and R _117. It may be formed.

Z ₁ and Z ₂ represent a methylene chain necessary for forming a condensed ring, and Z ₁ and Z ₂ may have a substituent (hydroxy group, alkoxy group, etc.).

Here, the number of carbon atoms contained in Z ₁ and Z ₂ is an integer of 2 to 8, preferably 3 to 6.

Specific examples of the compound represented by formula (B) according to the present invention are shown below, but the present invention is not limited thereto.

Many compounds of general formula (B) according to the present invention can be easily obtained as commercial products.

The addition amount of the compound of the general formula (B) is 1
Preferably 0.1 g to 50 g, more preferably 0.2 g to 20 g
Is.

The compound represented by formula (C) will be described in more detail.

In formula (C), the alkyl group represented by R ₁₀₄ , R ₁₀₅ and R ₁₀₆ preferably has 1 to 12 carbon atoms and may be linear, branched or cyclic (specifically, a methyl group). ，
Ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, t-amyl group, n-hexyl group, cyclohexyl group, etc.); alkenyl groups having 2 to 6 carbon atoms It may be straight-chain, branched-chain or cyclic (specifically, allyl group, isopropenyl group, cyclohexanyl group, etc.); aryl group having 6 to 12 carbon atoms is preferable (specifically, A phenyl group, a tolyl group, a naphthyl group, etc.); an aralkyl group having a carbon number of 7 to 12 is preferable (specifically, a benzyl group, a Pheneckel group, etc.); a heterocyclic group having a carbon number of 1 to 12 Preferred (specifically, imidazolyl group, pyrazolyl group, triazolyl group, pyridyl group, etc.).

R ₁₀₄ , R ₁₀₅ and R ₁₀₆ may have a substituent other than a hydrogen atom, and specific examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group. (Methyl group, ethyl group, butyl group, t-butyl group, methoxyethyl group, carboxymethyl group, hydroxyethyl group, etc.), aryl group (phenyl group, tolyl group, naphthyl group, etc.), alkoxy group (methoxy group, ethoxy group) Group, methoxyethoxy group, hydroxyethoxy group, etc.), aryloxy group (phenoxy group, p-nitrophenoxy group, etc.), sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzene) Sulfonamide group, etc.), sulfamoyl group, (unsubstituted sulfamoyl group, dimethylsulfamoyl) Group, ethylsulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.), ureido group (methylureido group,
Ethylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, methoxyethoxycarbonylamino group, etc.), acyl group (acetyl group, benzoyl group, etc.), formyl group,
Examples include cyano group, carboxy group, sulfo group, hydroxy group, nitro group, alkylthio group (methylthio group, hydroxyethylthio group, carboxymethylthio group, etc.), arylthio group (phenylthio group, etc.), and the number of substituents is 2 When there are more than one, they may be the same or different.

The nitrogen-containing heterocyclic group formed by linking R ₁₀₄ and R ₁₀₅ , R ₁₀₄ and R ₁₀₆ or R ₁₀₅ and R ₁₀₆ is a saturated or unsaturated 3 group.
The 8-membered ring may contain an oxygen atom and a sulfur atom in addition to the carbon atom and the nitrogen atom, and may be condensed with a benzene ring or a heterocycle. Specifically, an aziridine ring, an azetidine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring,
Pyrroline ring, imidazolidine ring, pyrazolidine ring, indoline ring, morpholine ring, pyrrole ring, imidazole ring, pyrazole ring, indole ring, indazole ring, triazole ring, tetrazole ring, phenoxylidine ring, tetrahydrothiazine ring, and the like. More preferably, it is a saturated or unsaturated 5- or 6-membered ring. Further, these nitrogen-containing heterocycles may have a substituent, and specific examples of the substituent include the same substituents as the above R ₁₀₄ , R ₁₀₅ and R ₁₀₆ .

The compound of the general formula (C) having a carboxy group in any of R ₁₀₄ , R ₁₀₅ and R ₁₀₆ preferably has 3 or more carbon atoms, and when any of R ₁₀₄ , R ₁₀₅ and R ₁₀₆ is a carboxyphenyl group. The substitution position of the amino group is preferably the meta position or para position of the carboxy group.

Specific examples of the compound represented by formula (C) are shown below, but the invention is not limited thereto.

C- (6) (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ C- (7) HNCH ₂ COOH) ₂ C- (9) H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ Specific examples other than the above include the compounds of Compound Examples (A-1) to (A-12) described in Japanese Patent Application No. 61-147823, pages 9 to 10, and No. 61-166674, page 10 to Compound Examples I- (1) to I- (22) described on page 14 and Compound Examples I- (1) to I- described on pages 11 to 14 of the specification No. 61-165621.
Examples thereof include the compound (21).

The compounds represented by the general formula (C) are disclosed in Japanese Patent Application No.
-147823, 61-166674, 61-165621, 61-1645
No. 15, 61-170789, 61-168159, 61-169789
No. 61-186561 and No. 61-197420, and the like.

The addition amount of the compound represented by the general formula (C) is preferably 0.05 g to 30 g, and more preferably 1 g per color developing solution.
It is 0.1 to 15 g.

The compound represented by formula (D) will be described in detail. In the formula (D), the unsubstituted alkyl group represented by R ₁₀₇ , R ₁₀₈ , R ₁₀₉ , R ₁₁₀ and R ₁₁₁ preferably has 1 to 10 carbon atoms and may be linear, branched or cyclic, and more preferably 1 to 6 carbon atoms
belongs to. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an n-hexyl group, a t-amyl group and a cyclohexyl group.

The unsubstituted alkylene group represented by R ₁₁₁ , R ₁₁₂ and R ₁₁₃ may be linear or branched having 1 to 6 carbon atoms, and specifically, methylene group, dimethylene group, trimethylene group, dimethyldimethylene group, Examples thereof include a tetramethylene group and a heptamethylene group.

The linking group for X ₁₂ and X ₁₃ includes -O- and -S- are preferred, and especially Is preferred.

R ₁₀₇ , R ₁₀₈ , R ₁₀₉ , R ₁₁₀ , and R ₁₁₄ may be the same or different, and R ₁₁₁ , R ₁₁₂ , and R ₁₁₃ may be the same or different.

Specific examples of the compound represented by formula (D) of the present invention are shown below, but the invention is not limited thereto.

D- (27) H ₂ NCH ₂ CH ₂ NH ₂ D- (28) H ₂ NCH ₂ CH ₂ CH ₂ NH ₂ D- (34) CH ₃ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ D- (35) CH ₃ NHCH ₂ CH ₂ NHCH ₃ D- (40) C ₆ H ₁₃ NHCH ₂ CH ₂ NH ₂ The addition amount of the compound represented by the general formula (D) is
It is preferably 0.05 g to 30 g, and more preferably 0.1 g to 15 g, per color developer.

These compounds can be synthesized by the method described in Japanese Patent Application No. 61-207545.

In the present invention, it is preferable that the color developing solution contains at least one compound selected from the group consisting of hydrazines, hydrazides and hydroxylamines, since the preservability of the color developing solution can be improved.

Preferred examples of hydrazines that can be used in the present invention include compounds represented by the following general formula (E).

General formula (E) (In the formula, R ₁₂₁ , R ₁₂₂ , R _123, and R ₁₂₄ are each independently a hydrogen atom, or a substituted or unsubstituted alkyl group,
It represents an aryl group or a heterocyclic group. R ₁₂₁ and R _122, and R ₁₂₃ and R ₁₂₄ may together form a heterocycle. Further, the substituents R ₁₂₁ , R ₁₂₂ , R ₁₂₃ and R ₁₂₄ may form a dimer or a multimer or more. ) The hydrazines represented by the general formula (E) are described in detail below.

General formula (E) In the formula, R ₁₂₁ , R ₁₂₂ , R ₁₂₃ and R ₁₂₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having a carbon number of 1 to 10, for example, a methyl group, an ethyl group, a hydroxyethyl group, cyclohexyl. Groups, benzyl groups, etc.),
A substituted or unsubstituted aryl group (preferably having 6 carbon atoms)
To 10, for example, a phenyl group, a 3-hydroxyphenyl group, a 4-methoxyphenyl group or the like) or a substituted or unsubstituted heterocyclic group (preferably having 1 to 10 carbon atoms, more preferably a 5 to 6-membered ring) Oxygen, nitrogen as atoms,
Those containing at least one of sulfur and the like, for example 4-
Pyridyl group, N-acetylpiperidin-4-yl group, etc.). R ₁₂₁ and R ₁₂₂ , and R ₁₂₃ and R ₁₂₄ may together form a heterocycle. Examples of the group further substituted on the substituents R _{121 to} R ₁₂₄ include a halogen atom (chlorine, bromine, etc.), a hydroxyl group, a carboxyl group, a sulfo group, an amino group, an alkoxy group, an amide group, a sulfonamide group,
A carbamoyl group, a sulfamoyl group, an alkyl group and an aryl group are preferable, and they may be further substituted.

In formula (E), preferred as R _{121 to} R ₁₂₄ are a hydrogen atom, an alkyl group and an aryl group. In particular, it is more preferable that R ₁₂₁ and R ₁₂₂ are both hydrogen atoms, and R ₁₂₃ and R ₁₂₄ are hydrogen atoms, an alkyl group or an aryl group, and R ₁₂₁ and R ₁₂₂ are hydrogen atoms and R ₁₂₃ and R ₁₂₄ are respectively. Most preferably, it is an alkyl group (R ₁₂₃ and R ₁₂₄ may together form a heterocycle).

When the compound represented by the general formula (E) is a monomer,
The total number of carbon atoms is preferably 10 or less, and 2 is preferable.
The case of 10 or more is more preferable, and the case of 2 or more and 7 or less is most preferable.

The compound of the general formula (E) may form a bis body, a tris body or a polymer linked by R ₁₂₁ , R ₁₂₂ , R ₁₂₃ and R ₁₂₄ .

Specific examples of the compound represented by formula (E) are shown below, but the invention is not limited thereto.

E- (2) CH ₃ NHNHCH ₃ E- (9) C ₂ H ₅ NHNHC ₂ H ₅ E- (12) HOOCCH ₂ NHNHCH ₂ COOH E- (13) NH ₂ NHCH _{2 3} NHNH ₂ E- (24) NH ₂ NHCH ₂ CH ₂ OH Many of the compounds represented by the general formula [E] are available as commercial products, and also "Organic Syntheses", Coll. Vol. , pp208 ~ 213
Can be synthesized according to.

The compound represented by the general formula [E] may form a salt with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid.

The amount of the compound represented by the general formula [E] added to the color developing solution is 0.1 g to 20 g per 1 color developing solution,
It is preferably 0.5 g to 10 g.

As a preferred example of the hydrazide which can be used in the present invention, a compound represented by the following general formula (F) can be obtained.

In the general formula _{(F) R 125 -X 14 -NHNH} -R 126 formula, X ₁₄ is -CO -, - SO ₂ - and Represents a divalent group selected from R ₁₂₅ is a hydroxyl group,
Hydroxyamino group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted hydrazinocarbonyl group,
A substituted or unsubstituted amino group (preferably having a carbon number of 0 to
10, for example, an amino group, a diethylamino group, a dipropylamino group, or the like, or a substituted or unsubstituted hydrazino group (preferably having 0 to 10 carbon atoms, for example, N ', N'-dimethylhydrazino group, N'- Phenylhydrazino group etc.)
Represents R ₁₂₅ is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having a carbon number of 1 to 10, for example, a methyl group, an ethyl group, a cyclohexyl group, a methoxyethyl group,
Benzyl group), a substituted or unsubstituted aryl group (preferably having 6 to 10 carbon atoms, for example, a phenyl group, p-
A tolyl group, a 2-hydroxyphenyl group, a 2-aminophenyl group, etc., a substituted or unsubstituted heterocyclic group (preferably having 1 to 10 carbon atoms, more preferably a 5 to 6-membered ring, and oxygen as a hetero atom, Those containing at least one of nitrogen and sulfur, for example, 4-pyridyl group, N-
Acetylpiperidin-4-yl group, etc.), a substituted or unsubstituted alkoxy group (preferably having a carbon number of 1 to 10, for example, methoxy group, ethoxy group, butoxy group, methoxyethoxy group, benzyloxy group, etc.), or substituted or unsubstituted Aryloxy group (preferably having 6 to 10 carbon atoms, for example, phenoxy group, p-methoxyphenoxy group, etc.). R ₁₂₆ is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having a carbon number of 6 to 10, such as a methyl group, an ethyl group, a cyclohexyl group, a methoxyethyl group) or a substituted or unsubstituted aryl group (preferably Carbon number 6
-10, for example, a phenyl group, a 3-hydroxyphenyl group, etc.).

Substituents R ₁₂₅ and R ₁₂₆ are further substituted as a halogen atom (for example, chlorine atom, bromine atom, etc.), hydroxyl group, carboxyl group, sulfo group, amino group, alkoxy group, amide group, sulfonamide group, A carbamoyl group, a sulfamoyl group, an alkyl group, an aryl group and the like are preferable, and they may be further substituted.

In formula (F), R ₁₂₅ is preferably an amino group, a hydrazino group, a hydrogen atom, an alkyl group, an aryl group or an alkoxy group.

In formula (F), R ₁₂₆ is preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom.

When the compound represented by the general formula (F) is a monomer,
The total carbon number is preferably 15 or less, 10
It is more preferably below, and most preferably 7 or below.

The compound of the general formula (F) may form a bis form, a tris form, or a polymer linked with R ₁₂₅ or R ₁₂₆ .

Specific examples of the compound represented by formula (F) are shown below, but the invention is not limited thereto.

F- (1) NH ₂ NHCONH ₂ F- (3) NH ₂ NHCONHNH ₂ F- (4) NH ₂ NHSO ₃ H F- (5) NH ₂ NHSO ₂ NHNH ₂ F- (6) NH ₂ NHCONHOH F- (9) CH ₃ NHNHSO ₂ NHNHCH ₃ F- (10) NH ₂ NHCONH- (CH ₂ ) ₃ -NHCONHNH ₂ F- (12) NH ₂ NHCONHCH ₃ F- (14) NH ₂ NH ₂ SO ₂ NHOH F- (16) NH ₂ NHCONHCONHNH ₂ F- (21) NH ₂ COCONHNH ₂ F- (22) NH ₂ NHCOCONHNH ₂ F- (24) NH ₂ NHCOOC ₂ H ₅ F- (25) NH ₂ NHCOCH ₃ F- (28) NH ₂ NHSO ₂ CH ₃ F- (30) CH ₃ NHNHCOOC ₂ H ₄ OCH _{3 F- (34) NH 2 NHCOCH 2} 4 CONHNH 2 F- (38) NH ₂ NHCHO F- (41) NH ₂ NHCOOC ₂ H ₄ OCONHNH ₂ F- (42) NH ₂ NHSO ₂ OC ₃ H ₇ (i) Many of the compounds represented by the general formula (F) are commercially available, or can be synthesized according to a general synthetic method such as “Organic Syntheses”, Coll. Vol. 2, p228. Is.

The compound represented by the general formula (E) may form a salt with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid.

The amount of the compound represented by the general formula (F) added to the color developing solution is 0.1 g to 20 g per color developing solution,
It is preferably 0.5 g to 10 g.

Preferred examples of hydroxylamines that can be used in the present invention include compounds represented by the following general formula (G).

General formula (G) In the formula, R ₁₂₇ and R ₁₂₈ represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

It is preferable that R ₁₂₇ and R ₁₂₈ are an alkyl group or an alkenyl group, and it is further preferable that at least one of them has a substituent. R ₁₂₇ and R ₁₂₈ may be linked to form a heterocycle together with the nitrogen atom.

The alkyl group or alkenyl group may be linear, branched or cyclic, and the substituents are halogen atoms (F, Cl, Br etc.), aryl groups (phenyl group, p-chlorophenyl group etc.), alkoxy groups (methoxy group). , Ethoxy group, methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.),
Sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.), ureido group (methylureido group, phenylureido group) Groups), alkoxycarbonylamino groups (methoxycarbonylamino groups, allyloxycarbonylamino groups (phenoxycarbonylamino groups, etc.), alkoxycarbonyl groups (methoxycarbonyl groups, etc.), aryloxycarbonyl groups (phenoxycarbonyl groups, etc.), cyano groups , Hydroxy group, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group), alkylthio group (such as methylthio group), arylthio group (such as phenylthio group), and het Ring group (morpholyl group, pyridyl group and the like) can be mentioned. Wherein R ₁₂₇ and R ₁₂₈ may be the same or different, may be Tsu different yet the same substituents R _127, R _128.

R ₁₂₇ and R ₁₂₈ preferably have 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the nitrogen-containing heterocycle formed by linking R ₁₂₇ and R ₁₂₈ include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group and a benztriazolyl group.

Preferred substituents for R ₁₂₇ and R ₁₂₈ are hydroxyl group, alkoxy group, sulfonyl group, amide group, carboxy group, cyano group, sulfo group, nitro group and amino group.

Specific examples of the compound represented by formula (G) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

The synthesis of the compound represented by the general formula (G) is carried out according to US Pat. Nos. 3,661,996, 3,362,961, 3,293,034, JP-B-42-2,794, US Pat. Nos. 3,491,151, 3,655,764,
3,467,711, 3,455,916, 3,287,125, 3,2
It can be synthesized by a known method shown in 87,124 or the like.

These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid. Other restoration agents can be selected from sugars, hydroxamic acids, α-hydroxyketones and the like.

The amount of these compounds added to the color developing solution is preferably 0.1 g to 20 g, more preferably 1 g per color developing solution.
It is 0.5g-10g.

In the present invention, a silver halide color photographic material is imagewise exposed, then subjected to the color development processing as described above, and subsequently processed with a processing solution having a bleaching ability.

Here, the processing solution having bleaching ability refers to a soluble silver salt such as a silver thiosulfate complex salt or an insoluble silver salt such as silver bromide by oxidizing metallic silver generated by a development reaction and colloidal silver contained in a light-sensitive material. And a processing solution having the ability to change the pH value, such as a bleaching solution or a bleach-fixing solution. In the present invention, it is preferable to perform processing with a processing solution having a bleach-fixing ability immediately after color development processing.

Examples of the bleaching agent used in the processing solution having a bleaching ability of the present invention include ferricyanic iron complex salts, ferric iron complex salts such as citrate and ferric iron complex salts, peroxides such as persulfates and hydrogen persulfide,
Examples of such oxidizing agents include ferric aminopolycarboxylic acid ferric complex salts, and complexes of ferric ions with aminopolycarboxylic acid or salts thereof.

As typical examples of these aminopolycarboxylic acids and salts thereof, diethylenetriaminepentaacetic acid diethylenetriaminepentaacetic acid pentasodium salt ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid trisodium salt ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-Triacetic acid triammonium salt 1,2-Diaminopropane tetraacetic acid 1,2-Diaminopropane tetraacetic acid disodium salt Nitrilotriacetic acid Nitrilotriacetic acid sodium salt Cyclohexanediaminetetraacetic acid Cyclohexanediaminetetraacetic acid disodium salt N-methyl -Iminodiacetic acid Iminodiacetic acid Dihydroxyethylglycine Ethyletherdiaminetetraacetic acid Glycoletherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid 1,3Diaminepropanetetraacetic acid Ethylenediaminetetraacetic acid, etc., but of course the invention is not limited to these exemplified compounds.

Among these compounds,
, And are particularly preferable.

The ferric aminopolycarboxylic acid complex salt may be used in the form of a complex salt of a complex salt, or a ferric salt such as ferric sulfate, ferric chloride, ferric sulfate, ammonium ferric sulfate, phosphoric acid. A second solution in solution using ferric iron and aminopolycarboxylic acid
An iron ion complex salt may be formed. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one or more ferric salts may be used. Furthermore, one or more aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of forming a ferric ion complex salt.

Aminopolycarboxylic acid Fe (III) other than the above
At least one complex salt and ethylenediaminetetraacetic acid Fe (II
It may be used in combination with I) a complex salt.

Further, the treatment solution having the bleaching ability containing the above-mentioned ferric iron complex salt may contain a metal ion complex salt of cobalt, nickel, copper or the like other than iron ion.

The amount of the bleaching agent per processing solution having a bleaching ability of the present invention is 0.1 mol to 1 mol, preferably 0.2 mol to 0.5 mol. The pH of the bleaching solution is preferably 4.0 to 8.0, more preferably 5.0 to 7.5.

In the treatment bath having a bleaching ability constituting the present invention, in addition to the bleaching agent and the above compound, a bromide such as potassium bromide,
A rehalogenating agent such as sodium bromide, ammonium bromide or chloride, such as potassium chloride, sodium chloride, ammonium chloride, may be included. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate,
Additives known to be commonly used in bleach-fixing solutions can be added, such as citric acid, sodium citrate, one or more inorganic acids having a pH buffering ability for tartaric acid, organic acids and salts thereof.

In the present invention, sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate may be added to a fixing bath subsequent to the bleaching bath or a processing bath having bleach-fixing ability.
Compounds known as fixing agents such as thiosulfates such as potassium thiosulfate, thiocyanates such as ammonium thiocyanate and potassium thiocyanate, thiourea and thioether can be contained. The amount of these fixing agents added is preferably 3 mol or less, and particularly preferably 2 mol, per processing solution having fixing ability or processing solution having bleach-fixing ability.
It is less than or equal to mol.

The processing solution having the bleach-fixing ability of the present invention includes, for example,
A so-called sulfite ion-releasing compound such as a sulfite or bisulfite such as sodium sulfite or ammonium sulfite, or an aldehyde-bisulfite adduct such as carbonyl bisulfite can be contained.

Further, aminopolycarboxylic acid salts represented by A-1 to A-24, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, 1,3diaminopropanetetrakismethylenephosphonic acid, nitrilo-N, N, N -Organophosphonic acid compounds such as trimethylenephosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid can be included.

In the present invention, the treatment liquid having the bleaching ability can be treated by containing at least one bleaching accelerator selected from a compound having a mercapto group or a disulphide bond, an isothiourea derivative and a thiazolidine derivative. . The amount of these compounds per one having the bleach-fixing ability is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol, particularly preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol. .

In the present invention, the bleaching accelerator to be contained during the bleaching treatment is a compound having a mercapto group or a disulphide bond, which is selected from a thiazolidine derivative, a thiourea derivative and an isothio derivative. What has an effect is good. Preferred examples include compounds represented by the general formulas (a) to (to) described in Japanese Patent Application No. 61-313598, pages 63 to 77, and specific examples.

In order to add these compounds to the treatment liquid, it is general to dissolve them in water, an alkali organic acid organic solvent or the like in advance and to add them, but immediately after the powder is added to a treatment bath having a bleaching ability. However, there is no effect on the bleaching promoting effect.

Further, in the present invention, a bleaching accelerator can be contained in the light-sensitive material. In this case, the bleaching accelerator can be contained in any of the blue, green and red emulsion layers or the gelatin layers such as the uppermost layer, the intermediate layer and the lowermost layer.

The processing bath having the bleach-fixing ability of the present invention may be a step consisting of one tank, but it may be a step consisting of two or more tanks, and the replenisher may be supplied in a multistage countercurrent system to the tank group. Alternatively, the replenisher may supply the replenisher to one bath of the tank group so that the treatment solution in the tank group is alternately circulated to form a uniform treatment solution as a whole.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering processing such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. this house,
The relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion
Picture of Television Engineers (Journal of the Society of Motion Picture and Tel
evision Engineers) Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material. Problems such as occur. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry and antifungal chemistry", The disinfectants described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Sanitary Technology Association, and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9 and preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected.

Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, JP-A-57-8543, 58-14834, 59-1843
43, 60-220345, 60-238832, 60-239784, 60-23
All known methods described in 9749, 61-4054, 61-118749 and the like can be used. In particular, 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, bismuth compound,
A stabilizing bath containing an ammonium compound or the like is preferably used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. .

Next, the silver halide color photographic light-sensitive material used in the present invention will be described. In the emulsion layer of the light-sensitive material, any silver halide of silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride and silver chloroiodide may be used. Silver iodobromide is preferred. In the case of silver iodobromide, the silver iodide content is usually 40 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less.

The silver halide grains may be so-called regular grains having regular crystals such as cubic, octahedral, and tetradecahedral, and may have irregular crystal forms such as spheres, twins, and the like. It may have a crystal defect such as a plane or a composite form thereof.

The silver halide may be a monodisperse emulsion having a narrow distribution or a polydispersant having a wide distribution.

Further, tabular grains having an aspect ratio of 5 or more may be used in the above emulsion layer.

The crystal structure of the above emulsion grains may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146, U.S. Patent Nos. 3,505,068, 4,444,
No. 877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image in both the surface and the inside. Further, the inside of the particles may be chemically sensitized.

The silver halide photographic emulsion which can be used in the present invention can be produced by appropriately using a known method, for example, Research Disclosure, Volume 176, No. 17643 (December 1978), 22-23.
Page, "I. Emulsion Preparation and Type
s) "and 187, No. 18716 (November 1979), 648
The method described on page can be followed.

In the preparation of the photographic emulsion of the present invention, various silver halide solvents (for example, ammonia, Rhodan Kali or U.S. Pat. No. 3,271,157, JP-A-51-12360 and JP-A-53-53 are optionally used.
It is also possible to use thioethers and thione compounds described in JP-A-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828.

The monodisperse emulsion is a silver halide grain having an average grain diameter of more than about 0.1 micron and at least 95
Emulsions are typically such that the weight percentage is within ± 40% of the average grain diameter. Have an average particle diameter of 0.25 to 2 microns and at least 95% by weight or (particle number) of at least
An emulsion in which 95% of silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc acid, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together.

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are described in Research Disclosure No. 17643 (December 1978) and No. 18716 described above.
(November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations described in the table below are shown.

As the spectral sensitizer used in the color photographic light-sensitive material of the present invention, the above-mentioned known sensitizers can be used.
In the processing method of the present invention, it is preferable to use the compounds represented by the general formula [IV] or [V] described in JP-A-313598, pages 90 to 110 and specific compounds.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. As the dye-forming coupler, a coupler that provides the three primary colors of the subtractive color method (that is, yellow, magenta and cyan) by color development is important,
RD17643, VII specific examples of equivalent or two equivalent couplers
-In addition to the couplers described in the patents mentioned in sections C and D,
The following can be preferably used in the present invention.

Typical examples of usable yellow couplers include known oxygen atom-releasing yellow couplers and nitrogen atom-releasing yellow couplers. α-
Pivaloyl acetanilide type couplers are excellent in color fastness of color forming dyes, especially light fastness, while α-benzoyl acetanilide type couplers can obtain high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye.

The cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-type and phenol-type couplers, and oxygen atom-elimination-type two-equivalent naphthol-type couplers are preferred as typical examples. Further, a coupler capable of forming a cyan dye that is robust against humidity and temperature is preferably used, and typical examples thereof include an alkyl group having an ethyl group or higher at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Having a phenolic cyan coupler, a 2,5-diacylamino-substituted phenolic coupler, a phenolic coupler having a phenylureido group at the 2-position and a siacylamino group at the 5-position, and the 5- coupler described in EP 161,626A. Examples include amide naphthol cyan couplers.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are specific examples of magenta couplers in U.S. Pat.No. 4,366,237 and the like, and yellow in European Patent No. 96,570 and the like.
Specific examples of magenta or cyan couplers are described.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. No. 3,451,820. Specific examples of the polymerized magenta coupler are described in US Pat. No. 4,367,282 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the above-mentioned RD17643, section VII-F are useful.

In the light-sensitive material of the present invention, a coupler which releases a nucleating agent or a development accelerator or a precursor thereof in an image-like manner during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. In addition, DIR described in JP-A-60-185950
Redox compound releasing couplers, such as the couplers described in EP 173,302A, which release dyes that recolor after release can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the steps of the latex dispersion method, effects, specific examples of latex for infiltration, U.S. Pat.
363, West German Patent Application (OLS) Nos. 2,541,274 and
No. 2,541,230.

The light-sensitive material used in the present invention, as a color antifoggant or color mixing inhibitor, hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, non-color couplers,
You may contain a sulfonamide phenol derivative etc.

A known anti-fading agent can be used in the light-sensitive material used in the present invention. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxy. Representative examples include benzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film usually used for photographic light-sensitive materials.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

(Examples) Hereinafter, the present invention will be illustrated by examples, but the present invention is not limited to these.

Example 1 Sample 101, which is a multi-layer color light-sensitive material consisting of each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal layers, also a coupler, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver …… 0.2 Gelatin …… 1.3 Coupler ExM-9 …… 0.06 UV absorber UV-1 …… 0.03〃 UV-2 …… 0.06〃 UV-3 …… 0.06 Dispersion oil Solv-1 …… 0.15 〃 Solv-2 …… 0.15 〃 Solv-3 …… 0.05 Second layer (intermediate layer) Gelatin …… 1.0 UV absorber UV-1 …… 0.03 Coupler ExC-4 …… 0.02 Compound ExF− 1 …… 0.004 Dispersed oil Solv-1 …… 0.1 〃 Solv-2 …… 0.1 3rd layer (low sensitivity red sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount …… 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Coating silver amount …… 0.6 Gelatin …… 1.0 Sensitizing dye ExS-1 …… 4 × 10 ^-4 〃 ExS-2 …… 4 × 10 ^-5 Coupler ExC-1 …… 0.05 〃 ExC-2 …… 0.50 〃 ExC-3 …… 0.03 〃 ExC-4 …… 0.12 〃 ExC-5 …… 0.01 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 1: 1 internal height) AgI type, sphere-corresponding diameter 0.7 .mu.m, coefficient of variation of 15% of the sphere-equivalent diameter, the plate-like particles, diameter / thickness ratio 5.0) coating silver amount ...... 0.7 gelatin ...... 1.0 sensitizing dye ExS-1 ...... 3 × 10 ^{- 4} 〃 ExS-2 …… 2.3 × 10 ^-5 Coupler ExC-6 …… 0.11 〃 ExC-7 …… 0.05 〃 ExC-4 …… 0.05 Dispersed oil Solv-1 …… 0.05 〃 Solv-3 …… 0.05 Fifth Layer (intermediate layer) Gelatin: 0.5 Compound Cpd-1: 0.1 Dispersion oil Solv-1: 0.05 Sixth layer (low sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1: 1) Internal high AgI type, sphere equivalent diameter 0.5μ, sphere equivalent diameter 15% dynamic coefficients, plate-like particles, diameter / thickness ratio 4.0) coating silver amount ...... 0.35 Silver iodobromide emulsion (AgI3 mol%, uniform AgI type, sphere-corresponding diameter 0.3
μ, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter / thickness ratio
1.0) Coating silver amount …… 0.20 Gelatin …… 1.0 Sensitizing dye ExS-3 …… 5 × 10 ^-4 〃 ExS-4 …… 3 × 10 ^-4 〃 ExS-5 …… 1 × 10 ^-4 Coupler ExM- 8 …… 0.4 〃 ExM-9 …… 0.07 〃 ExM-10 …… 0.02 〃 ExY-11 …… 0.03 Dispersed oil Solv-1 …… 0.3 〃 Solv-4 …… 0.05 7th layer (high sensitivity green emulsion layer) ) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type with core-shell ratio 1: 3, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 20%, plate-like grain, diameter / thickness ratio 5.0) coated silver amount …… 0.8 Sensitizing dye ExS-3 …… 5 × 10 ^-4 〃 ExS-4 …… 3 × 10 ^-4 〃 ExS-5 …… 1 × 10 ^-4 Coupler ExM-8 …… 0.1 〃 ExM-9… … 0.02 〃 ExY-11 …… 0.03 〃 ExC-2 …… 0.03 〃 ExM-14 …… 0.01 Dispersion oil Solv-1 …… 0.2 〃 Solv-4 …… 0.01 8th layer (intermediate layer) Gelatin …… 0.5 Compound Cpd-1 …… 0.05 Dispersed oil Solv-1 …… 0.02 9th layer (Multilayer effect for red-sensitive layer) Fruit donor layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type with core-shell ratio 2: 1, equivalent sphere diameter 1.0 μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 6.0 ) Coating amount of silver …… 0.35 Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type with 1: 1 core-shell ratio, sphere equivalent diameter 0.4μ, coefficient of variation of sphere equivalent diameter 20%, plate-like particles, diameter / thickness Ratio 6.0) Coating silver amount …… 0.20 Gelatin …… 0.5 Sensitizing dye ExS-3 …… 8 × 10 ^-4 Coupler ExY-13 …… 0.11 〃 ExM-12 …… 0.03 〃 ExM-14 …… 0.10 Dispersion oil Solv -1 ...... 0.20 10th layer (yellow coupler layer) Yellow colloidal silver ...... 0.05 Gelatin ...... 0.5 Compound Cpd-2 …… 0.13 〃 Cpd-1 …… 0.10 11th layer (low sensitivity blue sensitive emulsion layer) Iodour Silver halide emulsion (AgI 4.5 mol%, uniform AgI type, equivalent spherical diameter)
0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 7.0) Coating silver amount …… 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount …… 0.15 Gelatin …… 1.6 Sensitizing dye ExS-6 …… 2 × 10 ^-4 coupler ExC-16 …… 0.05 〃 ExC-2 …… 0.10 〃 ExC-3 …… 0.02 〃 ExY-13 …… 0.07 〃 ExY-15 …… 0.5 〃 ExC-17 …… 1.0 Dispersion oil Solv-1 …… 0.20 12th layer (high-sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type) , Sphere equivalent diameter
1.0μ, 25% variation coefficient of equivalent spherical diameter, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Coating silver amount …… 0.5 Gelatin …… 0.5 Sensitizing dye ExS-6 …… 1 × 10 ^-4 coupler ExY-15 …… 0.20 〃 ExY-13 …… 0.01 Dispersion oil Solv-1 …… 0.10 13th layer (1st protective layer) Gelatin …… 0.8 UV absorber UV-4 …… 0.1〃 UV-5 …… 0.15 Dispersion oil Solv-1 …… 0.01 〃 Solv-2 …… 0.01 14th layer 2 Protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.07μ) …… 0.5
Gelatin ...... 0.45 Polymethylmethacrylate particles 1.5μ ...... 0.2 Hardener H-1 ...... 0.4 Compound Cpd-3 ...... 0.5 Compound Cpd-4 ...... 0.5 Stabilization of emulsion in addition to the above components in each layer Agent Cpd-3
(0.04 g / m ² ) surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid. Other compounds Cpd-5 (0.5g /
^{m 2) ~Cpd-6 (0.5g} / m 2) was added.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Next, samples 102 to 105 were prepared by changing the couplers of the 3rd and 4th layers and / or the 6th and 7th layers to the couplers shown in Table 1 in equimolar amounts.

The samples 101 to 105 thus prepared were exposed to 20 CMS using an optical wedge, and then processed according to the following steps.

 Process Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ℃ Bleach-fixing 3 minutes 15 seconds 38 ℃ Water wash 40 seconds 35 ℃ Water wash 1 minute 00 seconds 35 ℃ Stability 40 seconds 38 ℃ Dry 1 minute 15 seconds 55 ℃ Next The composition of the treatment liquid is described in.

(Color developer) Diethylenetriamine pentaacetic acid 1.0 1-Hydroxyethylidene 3.0 1,1-Diphosphonic acid Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl-N- ( β-4.5 Hydroxyethyl) amino] -2-methylaniline sulfate Water was added to 1.0 l pH 10.05 The pH was adjusted by adding hydrochloric acid or potassium hydroxide.

(Bleach-fixing solution) Ferric ethylenediaminetetraacetic acid 50.0 Ammonium dihydrate Ethylenediaminetetraacetic acid dinatto 5.0 Lithium salt Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution 240.0 ml (70%) Ammonia water (27%) 6.0 ml pH 6.5 pH was adjusted using hydrochloric acid or aqueous ammonia (27%).

(Washing liquid) Tap water is passed through a mixed bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Then, the concentration of calcium and magnesium ions was adjusted to 3 mg / l or less, and subsequently 20 mg / l of sodium isocyanurate dichloride and 1.5 g / l of sodium sulfate were added.

 The pH of this solution was in the range 6.5-7.5.

(Stabilizer) Formalin (37%) 2.0 ml Polyoxyethylene-p-0.3 monononylphenyl ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Disodium salt water was added to 1.0 l pH 5.0-8.0 Then in color developer The same treatment was carried out by changing the sodium sulfite and the hydroxylamine sulfate of the above compounds to the compounds shown in Table 2 in equimolar amounts. The amount of residual silver in the maximum density portion of the obtained sample was measured by a fluorescent X-ray analysis method. The results are shown in Table 2. The maximum density of the magenta image at that time was measured, and the results are shown in Table 3.

As shown in Table 2, Comparative Sample 101 not containing the bleaching accelerator releasing compound of the present invention has a very high residual silver amount, and its influence is also seen in the maximum density of the magenta image.
The color density was very high. It is considered that this is because the density of the remaining silver is added to the density of the true magenta image, and thus the value becomes high. Therefore, although these color development densities are high and the results seem to be favorable, in reality, the image of residual silver is also viewed, which is extremely inconvenient in terms of color reproducibility.

In contrast, samples containing bleach accelerator releasing compounds
When 102 to 105 were treated with an ordinary color developing solution containing sodium sulfite ion (No. 1), an image having a slightly large amount of residual silver and low color density was obtained. In the case of treating with the liquids (No. 2 to No. 17), preferable results were obtained that the residual silver amount was small and the maximum concentration was high. Sample 10 containing no bleach accelerator releasing compound
The results of the present invention are surprising in that the amount of residual silver and the maximum concentration thereof when 1 is treated do not depend on the presence or absence of sulfite ion. In particular, when the color developing solution (No. 10 to 17) is processed by adding the exemplified compound represented by the general formula (E) or (F) in place of the hydroxylamine sulfate, the residual silver amount becomes smaller. The more preferable result that the maximum concentration is high was obtained.

Example 2 In the bleach-fix solution used in Example 1, the bleaching agent ethylenediaminetetraacetic acid ammonium ferric was changed to equimolar diethylenetriaminepentaacetic acid ferric ammonium, and otherwise the same treatment as in Example 1 was carried out. I did. The residual silver amount of the obtained sample was measured and summarized in Table 4.

The results obtained were the same as in Example 1.

Example 13 After exposing the samples 101 and 104 prepared in Example 1,
Each was processed by the following method using an automatic processor (until the cumulative replenishing amount of the bleach-fixing solution becomes 3 times the capacity of the mother liquor tank).

Next, the composition of the treatment liquid will be described. In addition, for the preparation of the treatment liquid,
Pure water was used. Pure water is the total concentration of dissolved ions
Distilled water and ion exchanged water below pm are shown.

(Bleach) Mother liquor, replenisher common (unit: g) Ethylenediamine 120.0 Ferric ammonium tetraacetate dihydrate Ethylenediamine 10.0 Tetraacetic acid disodium salt Ammonium bromide 100.0 Ammonium nitrate 10.0 Ammonia water (27%) 15.0 ml Add pure water 1.0l pH 6.3 The bleach overflow solution was led to the bleach-fix solution.

(Washing liquid) Common for mother liquor and replenishing liquid Tap water mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) Water was passed through a bed-type column to treat calcium and magnesium ions at a concentration of 3 mg / l or less, and then 20 mg / l sodium diisocyanurate dichloride and 1.5 g / l sodium sulfate were added.

 The pH of this solution was in the range 6.5-7.5.

(Stabilizer) Common for mother liquor and replenisher (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene 0.3-p-monononylphenyl ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Disodium salt 1.0 pH 5.0-8.0 Sample 101 is then treated in the above treatment step (treatment A)
The composition of the bleach-fixing solution was changed, and the others were similarly continuously processed (Process B). The composition of the newly used bleach-fixing solution was as follows.

Next, in Sample A, the composition of the bleaching solution in Treatment A was changed to the following composition, and the continuous treatment was performed in the same manner as in Treatment A (Treatment C).

Process C The overflow of the bleaching solution was led to the bleach-fixing solution.

Further, in the above-mentioned treatments A, B and C, the replenishing amounts of the bleaching solution and the bleach-fixing solution were each reduced by half, and the other treatments were continuously conducted in the same manner (treatments A ', B', C ').

In the above continuous processing, a sample exposed at 4800 ° K20 CMS was processed using an optical wedge in three stages of start, middle and end, and the residual silver amount and the maximum density of the magenta image at the maximum exposed portion were measured. The results are shown in Table 5.

As is clear from Table 5, according to the methods No. 2 and No. 6 of the present invention, the desilvering property is stable even in the continuous processing, and particularly, the stable desilvering is achieved even if the replenishment amount is reduced to 1/2. Silver performance was obtained. On the other hand, when the bleaching accelerator was added to the bleaching solution or the bleach-fixing solution, the desilvering performance deteriorated with continuous processing, and especially when the replenishment amount was reduced, the desilvering performance further deteriorated.

Example 4 Multilayer color light-sensitive material comprising each layer having the following composition on a subbed cellulose triacetate film support 20
Created 1.

First layer: antihalation layer Black colloidal silver 0.25 g / m ² UV absorber U-1 0.1 g / m ² UV absorber U-2 0.1 g / m ² High boiling organic solvent Oil-1 gelatin 1.9 g / m ² second layer: intermediate layer -1 Cpd D 10mg / m ² high-boiling organic solvent Oil-3 40 mg / m ² gelatin 0.4 g / m ² layer 3: fine silver iodobromide emulsion fogged the intermediate layer-2 surface (average particle size 0.06μ, AgI content 1 mol%) silver 0.05 g / m ² gelatin 0.4 g / m ² layer 4: spectrally sensitized with a first red-sensitive emulsion layer sensitizing dye S-1 and S-2 Silver iodobromide emulsion (1: 1 mixture of monodisperse cubes with average grain size 0.2μ and AgI content 5 mol% and monodisperse cubes with average grain size 0.1μ and AgI content 5 mol%) Silver amount 0.4 g / m ² coupler C-1 0.2 g / m ² 〃 C-2 0.05 g / m ² high-boiling organic solvent Oil-1 0.1 cc / m ² gelatin 0.8 g / m ² layer 5: 2nd red-sensitive emulsion layer up Silver iodobromide emulsion spectrally sensitized with dyes S-1 and S-2 (average AgI content of diameter 0.3 micron 4 mol% of monodisperse cubic emulsion) silver 0.4 g / m ² Coupler C-1 0.2 g / m ² 〃 C-3 0.2 g / m ² 〃 ^C-2 0.05g / m 2 High Boiling point organic solvent Oil-1 0.1 cc / m ² Gelatin 0.8 g / m ² 6th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average Monodisperse cube with a particle size of 0.4 μm and AgI content of 2 mol%) Silver amount 0.4 g / m ² Coupler C-3 0.7 g / m ² Gelatin 1.1 g / m ² 7th layer: Intermediate layer-3 Dye D-1 0.02 g / m ² gelatin 0.6 g / m ² 8th layer: Intermediate layer-4 Surface-fogged fine grain silver iodobromide emulsion (average grain size 0.06
μ, AgI content 1 mol%) Silver amount 0.05 g / m ² compound CpdA 0.2 g / m ² Gelatin 1.0 g / m ² 9th layer: 1st green sensitive emulsion layer Spectralized with sensitizing dyes S-3 and S-4 Sensitized silver iodobromide emulsion (1: 1 of a monodisperse cube having an average grain size of 0.2 μAgI content of 5 mol% and a monodisperse cube having an average grain size of 0.1 μAgI content of 5 mol%)
Mixture) Silver amount 0.5 g / m ² Coupler C-4 0.3 g / m ² Compound Cpd-B 0.03 g / m ² Gelatin 0.5 g / m ² 10th layer: 2nd green sensitive emulsion layer Sensitizing dye S-3 and Silver iodobromide emulsion containing S-4 (monodisperse cube having an average grain size of 0.4 μm and AgI content of 5 mol%) Silver amount 0.4 g / m ² coupler C-4 0.3 g / m ² compound Cpd B 0.03 g / m ² gelatin 0.6 g / m ² 11th layer: third green emulsion layer Sensitizing dyes Silver iodobromide emulsion containing S-3 and S-4 (AgI content 2 with an average grain size of 0.5 μ and an aspect ratio of 5) Mol%
Tabular emulsion) 0.5 g / m ² coupler C-4 0.8 g / m ² compound Cpd B 0.08 g / m ² gelatin 1.0 g / m ² 12th layer: intermediate layer-5 dye D-2 0.05 g / m ² gelatin 0.6 g / m ² 13th layer: yellow filter layer Yellow colloidal silver 0.1 g / m ² compound Cpd A 0.01 g / m ² gelatin 1.1 g / m ² 14th layer: 1st blue-sensitive emulsion layer Sensitizing dye A silver iodobromide emulsion containing S-5 and S-6 (a monodisperse cubic emulsion having an average grain size of 0.2 µ and an AgI content of 3 mol% and a monodisperse cubic emulsion having an average grain size of 0.1 µ and an AgI content of 3 mol%). 1: 1 mixture) Silver amount 0.6 g / m ² Coupler C-5 0.6 g / m ² Gelatin 0.8 g / m ² Fifteenth layer: second blue emulsion layer Contain sensitizing dyes S-7 and S-8 Silver iodobromide emulsion (tabular emulsion having an average grain size of 0.5 μ, aspect ratio of 7, AgI content of 2 mol%) Silver amount 0.4 g / m ² coupler C-5 0.3 g / m ² 〃 C-6 0.3 g / m ² gelatin 0.9 g / m ² 16th layer: third blue-sensitized emulsion layer sensitizing dye S-7 and S- Silver iodobromide emulsion containing (average particle size 1.0 micron, AgI content mol% of tabular emulsion having an aspect ratio 7) silver 0.4 g / m ² Coupler C-6 0.7 g / m ² Gelatin 1.2 g / m ² 17th layer: 1st protective layer UV absorber U-1 0.04g / m ² 〃 U-3 0.03g / m ² 〃 U-4 0.03g / m ² 〃 U-5 0.05g / m ² 〃 U-6 0.05 g / m ² compound CpdC 0.8 g / m ² dye D-3 0.05g / m ² gelatin 0.7 g / m ² 18th layer: fine silver iodobromide emulsion fogged the second protective layer surface (the average particle size 0.06μ, AgI content 1 mol%) Silver amount 0.1 g / m ² Polymethylmethacrylate particles (average particle size 1.5μ) 0.1 g / m ² Copolymer of methylmethacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.1 g / m ² Silicon oil 0.03 g / m ² Fluorine-containing surface active agent W-1 3 mg / m ² Gelatin 0.8 g / m ^{2 In} each layer, in addition to the above composition, gelatin hardener H-1 and Surfactant was added.

Oil 1 Dibutyl phthalate Oil 2 Tricresyl phosphate Next, the couplers C-1 and C-3 of the fourth, fifth and sixth layers are
Samples 202-206 were prepared by changing the coupler C-4 of the 9,10,11 layers and the couplers C-5 and C-6 of the 14,15,16 layers by equimolar amounts as shown in Table 7. Created.

The samples 201 to 206 prepared as described above were exposed to an exposure amount of 4800 ° K and 20 CMS using an optical wedge, and then processed according to the following steps.

Processing step G Processing step Time Temperature 1st development 6 minutes 38 ℃ First water wash 45 seconds 38〃 Reversal 45〃 38〃 Color development 6 minutes 38〃 Second water wash 45 seconds 38〃 Bleach fixing 4 minutes 38〃 Third Washing (1) 1〃 38〃 Third washing (2) 1〃 38〃 Stable 1〃 25〃 The composition of each treatment solution was as follows.

Third washing water Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite 1R-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite 1R-400). Water was added to control the calcium and magnesium ion concentration to 3 mg / l or less, and then 20 mg / l sodium diisocyanurate dichloride and 1.5 g / l sodium sulfate were added. The pH of this solution is in the range 6.5-7.5.

Then, the sodium sulfite in the color developing solution was changed to equimolar amounts of the compounds shown in Table 7, and the same treatment was carried out. The amount of residual silver in the minimum density part of the obtained sample was measured by a fluorescent X-ray analysis method. Also, measure the minimum concentration at that time,
The results are shown in Tables 7 and 8.

As is clear from Tables 7 and 8, it is found that the processing method of the present invention can obtain an image with a small amount of residual silver even in the reversal processing, and a great effect is particularly obtained in reducing the density of the highlight portion. It was

(Effects of the Invention) According to the present invention, in processing a silver halide photographic light-sensitive material containing a bleaching accelerator releasing compound, a very excellent bleaching promoting effect can be achieved and rapid processing becomes possible. The bleaching promoting effect can be stably maintained even when the light-sensitive material is subjected to continuous processing.

Further, according to the present invention, good photographic performance can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Ichishima 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (56) References JP-A-51-49725 (JP, A) JP-A-63-37346 ( JP, A) JP 63-70239 (JP, A) JP 63-70853 (JP, A) JP 61-201247 (JP, A) JP 63-73247 (JP, A) JP Sho 63-46455 (JP, A) JP 63-36245 (JP, A) JP 63-188136 (JP, A)

Claims (3)

[Claims] 1. A method in which a silver halide color photographic light-sensitive material is imagewise exposed, then color-developed, and then processed with a processing solution having a bleaching ability. The color developer contains a compound that reacts with the oxidant of the main agent to release a bleaching accelerator, and the concentration of sulfite ion and bisulfite ion in the color developer is 1 × 10 ^-2 mol or less (including 0). ) Is a processing method of a silver halide color photographic light-sensitive material. 2. The color developing solution comprises the following general formulas (A) to (D).
The treatment method according to claim (1), which contains at least one compound selected from the group of compounds represented by: General formula (A) (In the formula, R ₁₀₁ and R ₁₀₂ represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₀₃ represents a substituted or unsubstituted alkylene group. The total number of carbon atoms of R ₁₀₁ , R ₁₀₂ and R ₁₀₃ is 3 or more.) General formula (B) (In the formula, X ₁₁ represents a trivalent atom group necessary for completing the condensed ring. M ₁ represents an integer of 0 to 4, and n ₁ represents an integer of 1 to 5.) General formula ( C) (In the formula, R ₁₀₄ , R ₁₀₅ and R ₁₀₆ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Here, R ₁₀₄ and R ₁₀₅ ,
R ₁₀₄ and R ₁₀₆ or R ₁₀₅ and R ₁₀₆ may combine with each other to form a nitrogen-containing heterocycle. ) General formula (D) [In the formula, R ₁₀₇ , R ₁₀₈ , R ₁₀₉ and R ₁₁₀ each independently represent a hydrogen atom or an alkyl group, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ each independently represent an unsubstituted alkylene group, and X ₁₂ and X ₁₃ are independent -O -, - S -, - CO -, - SO 2 -, - SO- or represents a linking group composed of a combination of these linking groups (R
₁₁₄ represents a hydrogen atom or an alkyl group), m ₂ and n ₂ represent 0, 1, 2 or 3, respectively. ] 3. A color developing solution containing at least one compound selected from the group consisting of hydrazines, hydrazides and hydroxylamines. Processing method.