JPH0715567B2 - Silver halide photographic light-sensitive material and processing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material containing a bleach accelerator releasing type coupler.

BACKGROUND OF THE INVENTION Photographic materials useful in forming dye images by methods involving a bleaching step are known and used in the market.
Such materials and methods are described, for example, in The Theory of the Photographic Process.
f The Photographic Process), 4th edition, edited by TH James, pp. 462-463 and 335-361. The use of bleach accelerator releasing couplers in such photographic materials is described in Research Disclosure, 1973, Item No. 114.
49 and JP-A-61-201247.

However, the bleaching accelerator, which is a leaving group of these bleaching accelerator releasing couplers, has a certain effect in a state where the developing solution is unused, but the developing solution is usually used as a bleaching solution or a bleach-fixing solution. It was found that the bleaching promoting effect was considerably deteriorated in the running state.

This phenomenon is considered as follows.

The bleach released from the bleach accelerator releasing coupler in the developer is adsorbed on the developed silver.

The active species in this case can be said to be a thiol or a disfid body, but it is difficult to specify either. It is known that thiol produces disulphide by air oxidation etc. (especially fast in alkaline solution),
(New Chemical Chemistry Course, Volume 14 of the Chemical Society of Japan, P1735. Maruzen (1978)) It is speculated that disulphide may be formed during the development process.

It is known that the produced desilvering accelerator thiol or disulphide is attacked by sulfite ion present in the developer to produce thiol sulfonate.

(LCSchroeter "Sulfur Dioxide", p.145, Pergamon
It is described in Press (1966). Therefore, as described above, the deterioration of the bleaching-promoting effect in the running state means that the sulfite ion carried from the developer into the bleaching solution turns thiol or disulfide into a thiol-sulphonate ion, resulting in development silver. It is considered that the cause is that the adsorption power is weakened.

Therefore, these known bleach accelerator releasing couplers have insufficient bleach accelerating effect in the actual running state, and further improvement has been desired.

Further, couplers having a thioether group at the coupling position are described, for example, in US Pat. Nos. 3,227,554 and 4,293,691. These couplers were useful as so-called DIR couplers and 2-equivalent couplers, but their bleach-accelerating effect was insufficient, and some of them were rather deteriorated.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a novel bleaching accelerator releasing coupler which does not deteriorate the bleaching promoting effect even in a running state.

The second object is to provide a processing method of a silver halide color photographic light-sensitive material which has a high silver bleaching speed and can be processed rapidly.

The above object is to provide a silver halide photographic light-sensitive material containing a silver halide photographic emulsion layer and a bleach accelerator releasing coupler, wherein the bleach accelerator releasing coupler is represented by the following general formula (I). Achieved by a characteristic silver halide photographic light-sensitive material.

General formula (I) In the formula, A represents a coupler mother nucleus, TIME represents a timing group, n represents 0 or 1, R represents a trivalent aliphatic group having 8 or less carbon atoms, and X represents —OH, —CO ₂ M, −SO ₃ M
Or Represents Y, -SO ₃ M, Or represents -OR ₅ . Here, M represents a cation or a hydrogen atom, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or an aliphatic group or a phenyl group having a carbon number of 8 or less, and R ₅ is a fat having a carbon number of 8 or less. Represents a group or phenyl group.

The aliphatic group represented by R is a linear or branched, saturated or unsaturated, C 1-8 trivalent aliphatic group.

When R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > represent aliphatic groups, they are linear or cyclic, straight-chain or branched, saturated or unsaturated, aliphatic groups having 1 to 8 carbon atoms. Unsubstituted ones are preferable in synthesis, but may have a substituent in terms of performance, and typical substituents are —OH, —CO ₂ M, an alkoxy group having 1 to 3 carbon atoms or a halogen atom. Is mentioned. Here, M has the same meaning as described above.

Y is particularly preferably Is a group represented by.

When R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a phenyl group, the phenyl group is preferably unsubstituted, but may have a substituent, and a typical substituent is a methyl group, A methoxy group, a halogen atom, a hydroxyl group, an amino group or a carboxyl group can be mentioned. However, it is preferable that R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are not phenyl groups.

A typical example of R is When R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent an aliphatic group, typical examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an acyl group and a cyclohexyl group. Can be mentioned.

M is a hydrogen atom, sodium ion, potassium ion,
Typical examples are ammonium ion and pyridinium ion.

Examples of the coupler residue represented by A include 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, and a pyrazolotriazole type coupler residue). ), A cyan coupler residue (for example, a phenol residue, a naphthol type coupler residue, etc.), and a non-coloring coupler residue (for example, an indanone type, an acetophenone type coupler residue). Also, U.S. Pat.Nos. 4,315,070, 4,183,752, and 4,174,969.
No. 3,961,959 or 4,171,223.

The coupler residue is represented by the following general formula (Cp-1), (Cp-2),
(Cp-3), (Cp-4), (Cp-5), (Cp-6),
(Cp-7), (Cp-8), (Cp-8) or (Cp-9)
A more preferred example is a coupler residue represented by These couplers are preferred because of their high coupling speed. The free bond derived from the coupling position in the above formula represents the coupling position of the coupling-off group.

In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R
_{If 60} , R ₆₁ , R ₆₂ or R ₆₃ contains a diffusion resistant group, it is selected to have a total carbon number of 8 to 40, preferably 10 to 30, otherwise the total carbon number is It 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 carbon number may be out of regulation.

R _{51 to} R ₆₃ will be described in detail below with respect to d and e. 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 ₄₂
Has the same meaning as. R ₅₄ has the same meaning as R ₄₁ , 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 the 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 connected as a divalent group to form a cyclic structure. Examples of divalent groups for forming a cyclic structure are Is mentioned. Here, f represents an integer of 0 to 4, and g represents an integer of 0 to 2. R ₆₀ has the same meaning as R ₄₁ . R ₆₁ represents a group having the same meaning as R ₄₁ . R ₆₂ is R ₄₁
R ₄₁ CONH- group, R ₄₁ OCONH- group, R ₄₁ SO ₂ N
H-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 has 1 to 32 carbon atoms, preferably 1
To 22 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon groups. Typical examples are methyl group, ethyl group, propyl group,
Isopropyl group, butyl group, (t) -butyl group, (i)
-Butyl group, (t) -amyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, 1,1,3,
Examples thereof include a 3-tetramethylbutyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group.

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

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, 4-pyridyl group, 2-thienyl group,
2-furyl group, 2-imidazolyl group, pyrazinyl group, 2
-Pyrimidinyl group, 1-imidazolyl group, 1-indolyl group, phthalimido group, 1,3,4-thiadiazole-2-
Group, benzoxazol-2-yl group, 2-quinolyl group, 2,4-dioxo-1,3-imidazolidin-3-yl group, 2,4-dioxo-1,3-imidazolidin-3-yl group Group, succinimido group, phthalimido group, 1,2,4-triazol-2-yl group or 1-pyrazolyl group.

When the aliphatic hydrocarbon group, the aromatic group and the heterocyclic group have a substituent, a typical substituent is a halogen atom, R ₄₇ O— group, R ₄₆ S— group, 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, R ₄₇ , R ₄₈ and R ₄₉ are each an aliphatic group,
It represents 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, preferable 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 are preferably aromatic groups. R ₅₄ is an 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 preferably 1 or 2. 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 ₆₂ is R ₄₁ 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. R ₆₃
As R ₄₁ CONH- group, R ₄₁ SO ₂ NH- group, A nitro group or a cyano group is preferred.

Next, typical examples of R _{51 to} R ₆₃ will be described.

R ₅₁ is (t) -butyl group, 4-methoxyphenyl group, phenyl group, 3- {2- (2,4-di-t-amylphenoxy) butanamide} phenyl group, 4-octadecyloxyphenyl group or Examples include a methyl group. R ₅₂
And R ₅₃ is 2-chloro-5-dodecyloxycarbonylphenyl group, 2-chloro-5-hexadecylsulfonamidophenyl group, 2-chloro-5-tetradecanamidephenyl 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-tetra Decyloxycarbonylphenyl 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)
Examples thereof include a phenyl group, a 2-chlorophenyl group, and a 2-ethoxyphenyl group.

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-tetradecanamide anilino 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 Groups. R ₅₅ is a 2,4,6-trichlorophenyl group,
2-chlorophenyl group, 2,5-dichlorophenyl group, 2,3
-Dichlorophenyl group, 2,6-dichloro-4-methoxyphenyl group, 4- {2- (2,4-di-t-amylphenoxy) butanamide} phenyl group or 2,6-dichloro-4-methanesulfonyl group A phenyl 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, a 3-butylureido group, or 3- (2,4-di-t-amylphenoxy). A propyl group is mentioned. R ₅₇ is 3- (2,4-di-t
-Amylphenoxy) propyl group, 3- [4- {2-
[4- (4-hydroxyphenylsulfonyl) phenoxy] tetradecanamido} phenyl] propyl group, methoxy group, ethoxy group, methylthio group, ethylthio group, methyl group, 1-methyl-2- {2-octyloxy-5-
[2-octyloxy-5- (1,1,3,3-tetramethylbutyl) phenylsulfonamide] phenylsulfonamido} ethyl group, 3- {4- (4-dodecyloxyphenylsulfonamido) phenyl } Propyl group, 1,1-dimethyl-2- {2-octyloxy-5- (1,1,3,3-
Examples thereof include a tetramethylbutyl) phenylsulfonamido} ethyl group and 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-di-t-amylmethyl group, or furyl group. R ₅₉ is a chlorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, 2- (2,4-di-t-amylphenoxy) butanamide group, 2- (2,4-di-t-amylphenoxy) ) Hexanamide group, 2- (2,4-di-t-octylphenoxy) octanamide group, 2- (2-chlorophenoxy) tetradecanamide group, 2,2-dimethylpropanamide group, 2- { A 4- (4-hydroxyphenylsulfonyl) phenoxy} tetradecanamide group or a 2- {2- (2,4-di-t-amylphenoxyacetamido) phenoxy} butanamide group can be mentioned. R
₆₀ is a 4-cyanophenyl group, 2-cyanophenyl group, 4-butylsulfonylphenyl group, 4-propylsulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4-N, N-diethylsulfamoylphenyl group , 3,4
And a dichlorophenyl group or a 3-methoxycarbonylphenyl group. R ₆₁ includes dodecyl group, hexadecyl group, cyclohexyl group, butyl group, 3- (2,4
-Di-t-amylphenoxy) propyl group, 4- (2,
4-di-t-amylphenoxy) butyl group, 3-dodecyloxypropyl group, 2-tetradecyloxyphenyl group, t-butyl group, 2- (2-hexyldecyloxy)
Examples thereof include a phenyl group, a 2-methoxy-5-dodecyloxycarbonylphenyl group, a 2-butoxyphenyl group and a 1-naphthyl group. R ₆₂ is an isobutyloxycarbonylamino group, an ethoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfonamide group,
Examples thereof include a butanesulfonamide group, a 4-methylbenzenesulfonamide group, a benzamide group, a trifluoroacetamide group, a 3-phenylureido group, a butoxycarbonylamino group, and an acetamide group. R ₆₃ is a 2,4-di-t-amylphenoxyacetamide group,
2- (2,4-di-t-amylphenoxy) butanamide group, hexadecylsulfonamide group, N-methyl-N-
Octadecyl sulfamoyl group, N, N-dioctyl sulfamoyl group, dodecyloxycarbonyl group, chlor atom, fuso atom, nitro group, cyano group, N-3- (2,
4-di-t-amylphenoxy) propylsulfamoyl group, methanesulfonyl group or hexadecylsulfonyl group can be mentioned.

The group represented by TIME 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. When the group represented by TIME is used, the following known linking groups and the like can be mentioned.

(1) Group Utilizing Cleavage Reaction of Hemiacetal For example, a group described in US Pat. No. 4,146,396 and JP-A-60-249148 and 60-249149 and 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).

General formula (T-1) In the formula, W is an oxygen atom, a sulfur atom or 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 represents a divalent group and is also included when they are linked to each other 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, and E represents an electrophilic group.
Link is a group that can undergo a nucleophilic attack from Nu to cleave the bond with the ** symbol, 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) A group that utilizes an imino ketal cleavage reaction.

For example, it is a linking group described in US Pat. No. 4,546,073 and is a group represented by the following general formula.

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.

(Compound example) The coupler of the present invention can be synthesized by a known method or a similar method. For example, U.S. Pat.
1, 4,264,723, JP-A-55-29805, 55-25056
No. 55-29805 or 58-85864 can be used.

Next, a typical synthesis method will be described.

Synthesis Example (Synthesis of Exemplified Compound (1)) The compound was synthesized according to the following synthetic route.

29.4 g (i), 12.9 g (ii) and potassium carbonate 15.2
g to 200 ml of N, N-dimethylformamide and mixed at 80 ℃
Reacted for hours. The compound (ii) was post-treated and recrystallized from a mixed solvent of ethyl acetate and hexane to obtain the compound (ii
18.3 g of i) was obtained. By acid-hydrolyzing (iii) by a conventional method, 8.9 g of Exemplified compound (1) was obtained.

The coupler of the present invention can be added to the emulsion layer and the non-photosensitive intermediate layer. It is preferably contained in the emulsion layer. When it is added in a large amount, it is possible to reduce side effects such as sensitivity decrease by adding it to the non-photosensitive intermediate layer.

The addition amount is 0.01 mol% to 100 mol%, preferably 0.1 mol% to 50 mol%, and particularly preferably 1 mol% to 20 mol% of the total coated silver amount.

It is a preferred embodiment that the coupler of the present invention is used in combination with another color image forming coupler.

In the present invention, it is particularly preferable to use the compounds represented by the following general formulas [CC-1], [CC-2] and [CC-5] as the cyan coupler.

In the above formula, R ₁₁ is -CONR ₁₅ R ₁₆ , -NHCOR ₁₅ , -NHCOO.
R ₁₇ , -NHSO ₂ R ₁₇ , -NHCONR ₁₅ R ₁₆ or -NHSO ₂ NR ₁₅ R ₁₆
Represents

R ₁₅ , R ₁₆ and R ₁₇ represent an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms.

R ₁₂ is a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, an acyl group, R ₁₂ represents an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group or an imide group. The number of carbon atoms contained in is 0 to 30. p represents an integer of 0 to 3.

An example of cyclic R ₁₂ when p = 2 is a dioxymethylene group.

R ₁₃ is represented by the following general formula [CC-3].

R ₁₈ (Y ') q- ··· [CC-3] wherein Y' represents NH, CO or SO _2, q is zero or 1, R ₁₈ is a hydrogen atom, an aliphatic having 1 to 30 carbon atoms Group, aromatic group having 6 to 30 carbon atoms, heterocyclic group having 2 to 30 carbon atoms, -OR ₉ , -COR ₉ , -CO ₂ R _21, represents an -SO ₂ R ₂₁ or -SO ₂ OR _21,. Here, R ₁₉ , R ₂₀ and R ₂₁ have the same meanings as defined above for R ₁₅ , R ₁₆ and R ₁₇ , respectively.

At R ₁₁ or R ₁₈ R ₁₅ , R ₁₆ and R ₁₉ and R ₂₀ may be bonded to each other to form a nitrogen-containing heterocycle (morpholine ring, piperidine ring, pyrrolidine ring, etc.).

R ₁₄ represents an aliphatic group having 1 to 36 carbon atoms, an aromatic group having 6 to 36 carbon atoms or a heterocyclic group having 2 to 36 carbon atoms, preferably a tertiary alkyl group having 4 to 36 carbon atoms or a carbon number 7 to 36 are groups represented by the following general formula [CC-4].

In the formula, R ₂₂ and R _{23, which} may be the same or different, each represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms or an aromatic group having 6 to 30 carbon atoms, and R ₂₄ is a monovalent group. And Z'is -O
-, - S -, - SO- or -SO ₂ - represent. r is 0
When an integer of 5 is represented and r is plural, plural R ₂₄ may be the same or different. Preferred substituents are R ₂₂ and R
₂₃ is a linear or branched alkyl group having 1 to 18 carbon atoms, R ₂₄
Is a halogen atom, an aliphatic group, an aliphatic oxy group, a carbonamido group, a sulfonamide group, a carboxy group, a sulfo group, a cyano group, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an aliphatic oxycarbonyl group and an aromatic sulfonyl group. Z'can be each -O-. Here, the carbon number of R ₂₄ is 0 to 3, and r is preferably 1 to 3.

Ar represents a substituted or unsubstituted aryl group, which may be a condensed ring. Typical substituents for Ar include halogen atom, cyano group, nitro group, trifluoromethyl group, -CO
_{OR 25, -COR 25, -SO 2} OR 25, -NHCOR 25, -SO ₂ R ₂₇ , -SOR ₂₇ , -OCOR ₂₇ and Can be raised. R ₂₅ and R ₂₆ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₂₇ represents an aliphatic group, an aromatic group or a heterocyclic group. The carbon number of AR is 6 to 30, and a phenyl group having the above substituent is preferable.

X'represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of the coupling-off group are a halogen atom, -OR ₂₈ , -SR ₂₈ , -NHCOR ₂₈ , -NHSR ₂₈ , Aromatic azo group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms and nitrogen atom connected to the coupling active position of the coupler (succinimide group, phthalimido group, hydantoinyl group, pyrazolyl group, 2-benzo (Triazolyl group etc.)
And so on. Where R ₂₈ has 1 to 30 carbon atoms
Aromatic group of 6 to 30 carbon atoms or 2 to 2 carbon atoms
30 heterocyclic groups are shown.

As described above, the aliphatic group in the present invention is saturated / unsaturated,
It may be substituted / unsubstituted, linear / branched / cyclic, and typical examples include a methyl group, an ethyl group, a butyl group, a cyclohexyl group, an allyl group, a propargyl group,
Methoxyethyl group, n-decyl group, n-dodecyl group, n
-Hexadecyl group, trifluoromethyl group, heptalfluoropropyl group, dodecyloxypropyl group, 2,4-
Di-tert-amylphenoxypropyl group, 2,4-di-ter
A t-amylphenoxybutyl group and the like are included.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples are a phenyl group, a tolyl group, a 2-tetradecyloxyphenyl group, a pentafluorophenyl group,
2-chloro-5-dodecyloxycarbonylphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4
-Hydroxyphenyl group and the like are included.

Further, the heterocyclic group may be substituted or unsubstituted,
Typical examples are a 2-pyridyl group, a 4-pyridyl group,
A 2-furyl group, a 4-thienyl group, a quinolinyl group and the like are included.

In the above formula, R ₁₄ and X ′ have the same meanings as described in the general formula [CC-2].

The coupler represented by the general formula [CC-1] has a substituent R ₁₁ ,
The couplers represented by the general formulas [CC-2] and [CC-5] in R ₁₂ , R ₁₃ or X ′ are each represented by a divalent or divalent or more divalent group in the substituent R ₁₄ or X ′. Dimers, oligomers or higher multimers that bind to each other may also be formed. In this case, the carbon number range shown in each of the above substituents may be out of the range.

When the coupler represented by the general formula [CC-1], [CC-2] or [CC-5] forms a multimer, an addition-polymerizable ethylenic unsaturated compound having a cyan dye-forming coupler residue (cyan color forming A typical example is a homopolymer or a copolymer of (monomer). In this case, the multimer contains a repeating unit represented by the general formula [CC-6], and one or more cyan color-forming repeating units represented by the general formula [CC-6] may be contained in the multimer. It may be a copolymer containing one kind or two or more kinds of non-color forming ethylene type monomer as a polymerization component.

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, A ′ represents —CONH—, —COO— or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted An alkylene group, a phenylene group or an aralkylene group is shown, and L is -CONH-, -NHCONH-, -NHCOO.
-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO
-, - CO -, - O -, - S -, - SO 2 -, - NHSO 2 - or represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q is the general formula [CC-1], [CC-2] and [CC-5]
A cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the 1-position hydroxyl group is eliminated from the compound represented by

As the multimer, a copolymer of a cyan color-forming monomer giving a coupler unit of the general formula [CC-6] and the following non-color-forming ethylene-like monomer is preferable.

As the non-color-forming, ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent, acrylic acid,
α-Chloroacrylic acid, α-alkylacrylic acid (eg methacrylic acid) Esters or amides derived from these acrylic acids (eg acrylamide, methacrylamide, n-butylacrylamide, t)
-Butyl acrylamide, diacetone acrylamide,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate. And β-hydroxymethacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetate). (Phenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg. Vinyl ethyl ether), there maleate, N- vinyl-3-pyrrolidone, N- vinylpyridine and 2- and 4-vinylpyridine and the like.

Acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds, and maleic acid esters are particularly preferable. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

Next, specific examples of the couplers represented by the general formulas [CC-1], [CC-2], [CC-5] and [CC-6] are shown, but the couplers used in the present invention are not limited thereto. Not a thing. The following in formula (t) C ₅ H ₁₁ is _{-C (CH 3) 2 C 2} H 5,
(t) C ₈ H ₁₇ represents -C a _{(CH 3) 2 CH 2 C} (CH 3) 3 , respectively.

The coupler represented by the general formula [CC-1] is disclosed in Japanese Patent Application No. 59-936.
It is synthesized by the method described in No. 05, No. 59-264277 and No. 59-268135.

The coupler represented by the general formula [CC-2] is a US patent (U
S) 3488193, JP-A-48-15529, 50-117422,
52-18315, 52-90932, 53-52423, 54-482
No. 37, No. 54-66129, No. 55-32071, No. 55-65957, No.
55-105226, 56-1938, 56-12643, 56-27147
No. 56-126832 and No. 58-95346.

The coupler represented by the general formula [CC-5] is described in US Pat.
No. 254,212, No. 4,296,199, No. 3,488,193, British Patent No. 914,507, and Japanese Patent Publication No. 54-37822.

The total addition amount of the couplers represented by the general formulas [CC-1], [CC-2] and [CC-5] is within the range of all cyan couplers.
It is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol%, further preferably 90 mol% or more.

These general formulas [CC-1], [CC-2] and [CC-5]
It is preferable to use two or more types of couplers represented by the above formula. When the same color-sensitive layer is divided into two or more layers having different sensitivities, 2 equivalents of the cyan coupler is used for the high-grade layer and 4 equivalents of the low-sensitivity layer. It is preferable to use a cyan coupler.

Any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention.

The silver halide grains in a photographic emulsion have regular crystal forms such as cubes, octahedra and tetradecahedrons, irregular crystal forms such as spheres and plates, and twin planes. It may have a crystal defect such as or a composite form thereof.

The grain shape of the silver halide may be fine grains of about 0.1 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978.
December), pp. 22-23, "I. Emulsion preparati
on and types) ”and the same, No.18716 (November 1979),
648 pages, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chimie et Physique Photogr
aphique Paul Montel, 1967), “Photoemulsion Chemistry” by Duffin, published by Forcal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966), “Production and Coating of Photographic Emulsions” by Selikman et al., VLZelikman et al, Making and Coating Photogra
Phic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are written by Gatov,
Gutoff, Photographic Science and Engineerin
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide.

Also, a mixture of particles having various crystal forms may be used. The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two research disclosures, and the locations described in the table below are shown.

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.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
Those described in No. 52, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 2,476,760 are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloar-based compounds are preferable, and US Pat.
619, 4,351,897, European Patent 73,636, U.S. Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (6 June 1984)
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol type and naphthol type couplers, and U.S. Pat. No. 4,052,212;
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,365A, U.S. Patent No. 3,4.
46,622, 4,333,999, 4,451,559, 4,
Those described in 427,767, EP 161,626A and the like are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure No. 17643 VII-
Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No. 1,
Those described in No. 146,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is RD17643, the patents described in the above paragraphs VII to F, JP-A-57-151944 and JP-A-57-154234,
Those described in US Pat. No. 60-184248 and US Pat. No. 4,248,962 are preferable.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent Nos. 2,097,140 and 2,1
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427 and the like, multiequivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-18
DIR redox compound releasing coupler described in No. 5950,
Examples thereof include couplers that release a dye that restores color after separation described in EP 173,302A.

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.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same, No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD, No. 1
Development can be carried out by a usual method described in pages 28 to 29 of 7643 and 651 left column to right column of No. 18716.

The silver halide photographic light-sensitive material of the present invention is preferably processed in a bleach-fixing bath after color development without washing with water.

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 process 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 (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. Therefore, it can be set in a wide range. Among these, the relationship between the number of flush tanks and the water volume in the multi-stage countercurrent system is as follows: Journal of the Society of Motion Picture and Television Engineers (Jo
urnal of the Society of Motion Picture and Televis
ion Engineers) Volume 64, P.248-253 (May 1955 issue)
It can be obtained by the method described in.

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, the method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively as a solution to such a problem.
Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based germicides such as chlorinated sodium isoannurate, and other benzotriazoles,
Horiguchi Hiroshi "Chemistry of Antibacterial and Antifungal Agents", Sanitary Technology Association, "Microbial Sterilization, Sterilization, Antifungal Technology", Japan Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" Can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The temperature of washing water and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15-45 ° C, and preferably 30 at 25-40 ° C.
A range of seconds-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, JP-A-58-14834, and JP-A-59-18
No. 4343, No. 60-220345, No. 60-238832, No. 60-239784
All known methods described in No. 60-239749, No. 61-4054, No. 61-118749, etc. can be used. In particular, 1-hydroxyethylidene-1,1-diphosphonic acid,
A stabilizing bath containing 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound and the like is preferably used.

Further, there is a case where further stabilizing treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. .

Next, regarding the rinse bath or stabilizing bath that can be used in the present invention,
Details will be described.

Between the rinse bath or stabilizing bath and the bath having a fixing ability, there may be a short washing with water or rinsing, if necessary. The "bath having a fixing ability" in the present invention mainly means a conventional bleach-fixing bath or a fixing bath, and these baths preferably contain a thiosulfate as described later.

The rinse bath is mainly used to wash out the processing liquid components adhering to or occluded in the color light-sensitive material, and the constituent components of the color light-sensitive material to be removed in order to secure the photographic performance after processing and the stability of the image. It is the intended bath.

Further, the stabilizing bath refers to a bath having an image stabilizing function which cannot be obtained by the rinse bath in addition to the function as the rinse bath, and for example, a bath containing formalin corresponds thereto. What is the amount brought in from the front bath?
It means the capacity of the pre-bath that is attached to and absorbed by the light-sensitive material and is mixed in the rinse bath.The color light-sensitive material collected just before entering the rinse bath is immersed in water to extract the pre-bath components, It can be calculated by measuring the amount of bath components.

The rinsing bath or stabilizing bath of the present invention is preferably a countercurrent system of two or more stages, and the replenishing amount is 0.5 to 50 times, preferably 1.0 to 30 times the carry-in amount from the previous bath per unit area of the light-sensitive material. It is less than 1/10 of the amount of water.

The rinsing bath or stabilizing bath of the present invention may contain various antibacterial agents and antifungal agents in order to prevent the generation of water stains and the mold generated in the light-sensitive material after processing. Examples of these antibacterial agents and antifungal agents include JP-A-57
-157244 and 58-105145, a thiazolylbenzimidazole compound, or JP-A-57-8
No. 542 isothiazolone compounds, or chlorophenol compounds typified by trichlorophenol, or promophenol compounds, or organotin or organozinc compounds, or
Proposed thiocyanate, isothiocyanic acid-based compound, acid amide-based compound, diazine or triazine-based compound, thiourea-based compound, benzotriazole alkylguanidine compound, or quaternary compound represented by benzalkonium chloride Ammonium salts or antibiotics such as penicillin, Journal Anti-bacteria
Anteif Angus Agent (J.Antibact.Antif
ung.Agents) Voll, No. 5, p-207 to 223 (1983), one or more general-purpose antifungal agents may be used in combination.

Also, various fungicides described in JP-A-48-83820 can be used.

The softening-treated water can be used for the rinse liquid or the stabilizing liquid. Examples of the water softening treatment method include using an ion exchange resin or a reverse osmosis device.

As the ion exchange resin, a sodium type strong acid cation exchange resin in which the counter ion of the exchange group is sodium is preferable, and an H type strong acid cation exchange resin and an ammonium type strong acid cation exchange resin can also be used. Further, it is also preferable to use an H-type strongly acidic cation exchange resin and an OH-type strongly basic anion exchange resin in combination. As the resin substrate, a copolymer of styrene and divinylbenzene is preferable, and the amount of divinylbenzene charged during production is 4 to 16% of the total amount of monomers charged.
(W / w) is preferable.

As an example of such an ion exchange resin, Mitsubishi Kasei Co., Ltd.
The trade name of Diaion SK-1B or PK-216 can be mentioned.

Although various types of reverse osmosis devices can be used, those using a cellulose acetate or polyether sulfone membrane are suitable. When the pressure is 20 kg / m ² or less, noise is small and it is easy to use.

By using such an ion exchange resin or a reverse osmosis treatment apparatus, water in which calcium and magnesium are reduced causes less growth of bacteria and mold, and by combining with the present invention, good results can be obtained. is there.

It is preferable to add a chelating agent to the rinsing bath or stabilizing bath of the present invention from the viewpoint of liquid stability. Examples of the chelating agent include inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid and phosphonocarboxylic acid.

(Examples) Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of Photosensitive Layer) The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

1st layer (anti-halation layer) Black colloidal silver …… 0.2g / m ² Gelatin …… 1.3g / m ² Colored coupler C-1 …… 0.06g / m ² UV absorber UV-1 …… 0.1g / m ² Same as above UV-2 …… 0.2 g / m ² High boiling point organic solvent Oil-1 …… 0.01 CC / m ² Same as above Oil-2 …… 0.01 CC / m ² Second layer (intermediate layer) Fine silver bromide (average) Particle size 0.07μ) …… 0.15g / m ² Gelatin …… 1.0g / m ² Colored coupler C-2 …… 0.02g / m ² High boiling point organic solvent Oil-1 …… 0.1CC / m ² 3rd layer ( Low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.3 µ)
Silver 0.4g / m ² Gelatin …… 0.6g / m ² Sensitizing dye I …… 1.0 × 10 ^-4 Sensitizing dye II …… 3.0 × 10 ^-4 Sensitizing dye III …… 1 × 10 ^-5 Coupler C- 3 …… 0.06g / m ² coupler C-4 …… 0.06g / m ² coupler C-8 …… 0.04g / m ² coupler C-2 …… 0.03g / m ² high boiling organic solvent Oil-1 …… 0.03CC / m ² Same as above Oil-3 …… 0.012CC / m ² 4th layer (medium speed red emulsion layer) Silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.5μ) ……
0.7g / m ² sensitizing dye I …… 1 × 10 ^-4 sensitizing dye II …… 3 × 10 ^-4 sensitizing dye III …… 1 × 10 ^-5 coupler C-3 …… 0.24g / m ² coupler C-4 …… 0.24g / m ² coupler C-8 …… 0.04g / m ² coupler C-2 …… 0.04g / m ² high boiling organic solvent Oil-1 …… 0.15CC / m ² Same as above Oil-3 …… 0.02CC / m ² 5th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.7μ) ……
Silver 1.0 g / m ² gelatin …… 1.0 g / m ² Sensitizing dye I …… 1 × 10 ^-4 Sensitizing dye II …… 3 × 10 ^-4 Sensitizing dye III …… 1 × 10 ^-5 Coupler C- 6 …… 0.05g / m ² Coupler C-7 …… 0,1g / m ² High boiling point organic solvent Oil-1 …… 0.01CC / m ² Same as above Oil-2 …… 0.05CC / m ² 6th layer (intermediate Layer) Gelatin: 1.0 g / m ² compound Cpd-A: 0.03 g / m ² High boiling point organic solvent Oil-1: 0.05 CC / m ² 7th layer (low sensitivity green emulsion layer) Silver iodobromide Emulsifier (4 mol% silver iodide, average particle size 0.3μ)
… 0.30 g / m ² Sensitizing dye IV …… 1 × 10 ^-4 Sensitizing dye VI …… 0.3 × 10 ^-4 Sensitizing dye V …… 2 × 10 ^-4 Gelatin …… 1.0 g / m ² Coupler C- 9 ...... 0.2g / m ² coupler C-5 ...... 0.03g / m ² coupler C-1 ...... 0.03g / m ² high-boiling organic solvent Oil-1 ...... 0.5CC / m ² eighth layer (middle sensitivity Green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.5 µ)
0.4g / m ² sensitizing dye IV …… 5 × 10 ^-4 sensitizing dye V …… 2 × 10 ^-4 sensitizing dye VI …… 0.3 × 10 ^-4 coupler C-9 …… 0.25g / m ² coupler C-1 ...... 0.03g / m ² coupler C-10 ...... 0.015g / m ² coupler C-5 ...... 0.01g / m ² high-boiling organic solvent Oil-1 ...... 0.2CC / m ² 9th layer ( High-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7μ)
Silver 0.85 g / m ² Gelatin …… 1.0 g / m ² Sensitizing dye VII …… 3.5 × 10 ^-4 Sensitizing dye VIII …… 1.4 × 10 ^-4 Coupler C-11 …… 0.01 g / m ² Coupler C- 12 …… 0.03g / m ² coupler C-13 …… 0.20g / m ² coupler C-1 …… 0.02g / m ² coupler C-15 …… 0.02g / m ² high boiling organic solvent Oil-1 …… 0.20CC / m ² Same as above Oil-2 …… 0.05CC / m ² 10th layer (yellow filter layer) Gelatin …… 1.2g / m ² Yellow colloidal silver …… 0.08g / m ² Compound Cpd-B …… 0.1g / m ² High boiling point organic solvent Oil-1 …… 0.3 CC / m ² 11th layer (low sensitivity blue sensitive emulsion layer) Monodisperse silver iodobromide emulsion (4 mol% silver iodide, average grain size 0.3
μ) Silver 0.4g / m ² Gelatin 1.0g / m ² Sensitizing dye IX 2 × 10 ^-4 Coupler C-14 0.9g / m ² Coupler C-5 0.07g / m ² High boiling point organic solvent Oil-1 …… 0.2CC / m ² 12th layer (high sensitivity blue emulsion layer) Silver iodobromide (silver iodide 10 mol%, average grain size 1.5μ) …… Silver 0.5
g / m ² Gelatin …… 0.6g / m ² Sensitizing dye IX …… 1 × 10 ^-4 Coupler C-14 …… 0.25g / m ² High boiling point organic solvent Oil-1 …… 0.07CC / m ² 13th Layer (first protective layer) Gelatin: 0.8g / m ² UV absorber UV-1: 0.1g / m ² Same as above UV-2: 0.2g / m ² High boiling organic solvent Oil-1: 0.01CC / m ² Same as above Oil-2 …… 0.01CC / m ² 14th layer (2nd protective layer) Fine grain silver bromide (average grain size 0.07μ) …… 0.5g / m ² Gelatin …… 0.45g / m ² Poly methyl acrylate particles (diameter 1.5μ) ...... 0.2g / m ² hardener H-1 ...... 0.4g / m ² of formaldehyde scavenging Ja S-1 ...... 0.5g / m ² of formaldehyde scavenging Ja S-2 ...... 0.5 In addition to the above components, a surfactant was added to each layer of g / m ² as a coating aid. The sample prepared as described above is sample 101
And

The chemical structural formulas or names of the compounds used in the present invention are shown below: Oil-1 Tocresyl phosphate Oil-2 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate The sample manufactured as described above was designated as 101.

Preparation of Samples 102 to 110 Samples 102 to 110 were prepared in the same manner as in Sample 101, except that the couplers shown in Table 1 were replaced by equimolar amounts of the couplers C-3 of the third and fourth layers.

Samples 101 to 110 are cut to a width of 35 m / m, a standard subject is photographed, and each of the following 5 processing steps (I) to (III)
I ran a running test of 00m. After the running was completed, the samples 101 to 110 were exposed to white light at 20 CMS and subjected to the following development processing.

Table 1 shows the results of fluorescent X-ray analysis of the residual silver content of the developed sample.

It can be seen that when the coupler of the present invention is used, the desilvering promoting effect is sufficiently exhibited even in the running state.

In the above treatment process, a stable, countercurrent system of →→ was adopted. The amount of fixer brought into the washing tank was 2 ml per 1 m.

In the above treatment step, the washing with water was a countercurrent washing method from to. Next, the composition of each processing liquid will be described.

<Bleach-fixing solution> Common for mother liquor and replenishing solution Ethylenediaminetetraacetic acid ferric ammonium salt 50.0g Ethylenediaminetetraacetic acid disodium salt 5.0g Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70%) 240ml Add ammonia water to make pH7.3 water. In addition, 1 << Rinsing water >> As washing water, tap water was passed through a column filled with Na-type strongly acidic cation exchange resin (Diaion SK-1B manufactured by Mitsubishi Kasei Co., Ltd.) to obtain calcium mg / l and magnesium. 1.2m
The water quality of g / l was used.

<< Stabilizer >> Same as process step (I) << Washing Water >> The following three types were used.

(1) Tap water Calcium 26 mg / l Magnesium 9 mg / l pH 7.2 (2) Ion exchange treated water The above tap water was treated with a strongly acidic cation exchange resin (Na type) manufactured by Mitsubishi Kasei Co., Ltd. did.

Calcium 1.1 mg / l Magnesium 0.5 mg / l pH 6.6 (3) Chelating agent-added tap water To the tap water, 500 mg / l of ethylenediaminetetraacetic acid secondary sodium salt was added.

pH 6.7 The process and the treatment liquid were carried out as described above.

Practically, it is known that when the residual silver amount exceeds 30 mg / m ² , the performance is largely deteriorated in color reproduction and / or gradation balance. As is clear from the above table, it can be seen that the use of the compound of the present invention is in a range where there is no practical problem even in rapid processing.

Example 2 A multilayer photosensitive material having the following layers was prepared on a support similar to that of Example 1 to obtain Sample 201.

First layer (anti-halation layer) Black colloidal silver 0.2 Gelatin 1.0 Ultraviolet absorber UV-1 0.2 High boiling organic solvent Oil-1 0.02 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) 0.15 Gelatin 1.0 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.3 μ) 1.5 Gelatin 0.9 Sensitizing dye A 1.0 × 10 ⁻⁴ Sensitizing dye B 2.0 × 10 ^{− 4} Coupler D-1 0.6 Coupler D-2 0.2 Coupler D-3 0.02 Coupler D-4 0.01 High boiling point organic solvent Oil-1 0.1 Same as above Oil-2 0.1 Fourth layer (high-sensitivity red-sensitive emulsion layer) Monodisperse iodobromide Silver emulsion (silver iodide 5 mol%, average grain size 0.7
μ) 1.2 Gelatin 1.0 Sensitizing dye A 3 × 10 ^-4 Sensitizing dye B 2 × 10 ^-4 Coupler D-1 0.10 Coupler D-2 0.03 Coupler D-5 0.01 Coupler D-4 0.02 Coupler D-3 0.02 High boiling point Organic solvent Oil-2 0.1 Fifth layer (intermediate layer) Gelatin 1.0 Compound Cpd-A 0.05 High boiling point organic solvent Oil-2 0.05 Sixth layer (low-sensitivity green emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide) 3 mol%, average particle size 0.3
μ) 0.6 Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.5
μ) 0.7 Gelatin 1.0 Sensitizing dye C 3 × 10 ^-4 Sensitizing dye D 2 × 10 ^-4 Coupler D-6 0.4 Coupler D-7 0.1 Coupler D-8 0.02 Coupler D-9 0.01 High boiling organic solvent Oil-2 0.05 7th layer (high-sensitivity green-sensitive layer) Polydisperse silver iodobromide emulsion (7 mol% silver iodide, average grain size 0.8)
μ) 0.8 Gelatin 0.9 Sensitizing dye C 2 × 10 ^-4 Sensitizing dye D 1.5 × 10 ^-4 Coupler D-6 0.08 Coupler D-7 0.05 Coupler D-9 0.02 High boiling point organic solvent Oil-1 0.08 Same as above Oil-3 0.03 8th layer (intermediate layer) Gelatin 1.2 Compound Cpd-A 0.6 Dispersion oil Oil-1 0.3 9th layer (Yellow filter layer) Yellow colloidal silver 0.1 Gelatin 0.8 Compound Cpd-A 0.2 High boiling organic solvent Oil-1 0.1 10th Layer (low-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.3)
μ) 0.3 Monodisperse silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.6
μ) 0.3 Gelatin 1.0 Sensitizing dye E 1 × 10 ^-4 Sensitizing dye F 1 × 10 ^-4 Coupler D-10 0.9 Coupler D-4 0.05 High boiling organic solvent Oil-3 0.01 11th layer (high sensitivity blue sensitive emulsion) Layer) Monodisperse silver iodobromide emulsion (8 mol% silver iodide, average grain size 1.5)
μ) 0.7 Gelatin 0.5 Sensitizing dye E 5 × 10 ^-4 Sensitizing dye F 5 × 10 ^-4 Coupler D-10 0.2 Coupler D-4 0.05 High boiling point organic solvent Oil-3 0.01 12th layer (first protective layer) Gelatin 0.5 Fine grain silver bromide emulsion (average grain size 0.07μ) 0.33 Coupler D-11 0.1 UV absorber UV-2 0.1 UV absorber UV-3 0.2 High boiling organic solvent Oil-4 0.01 13th layer (2nd protective layer) ) Gelatin 0.8 Polymethylmethacrylate particles (diameter 1.5 μm) 0.2 Formaldehyde vengeer H-1 10.5 In addition, surfactant W-1 and hardener H-1 were added.

The third layer in hardness agent _{H-1 CH 2 = CHSO 2} (CH 2) 3 SO 2 CH = CH 2 prepared sample 201 of the sample 202 to 210, shown in Table 1 in place of the coupler D-1 of the fourth layer It was prepared in the same manner as Sample 201 except that the coupler was replaced with an equimolar amount.

Samples 211 to 215 Samples 211 to 215 were prepared in the same manner as in Sample 201 except that the couplers shown in Table 1 were replaced by the equimolar amounts of the couplers D-6 of the sixth and seventh layers. The obtained sample was used in Example 1.
After the running treatment of the treatment step (III) was carried out in the same manner as in (1), the treatment was stripped and exposed to 20 CMS, and the residual silver amount was measured.

The results are shown in Table 2.

It can be seen that when the couplers of the present invention are used, the residual silver amount is small and the bleaching promoting effect is sufficiently exerted even in the running state.

(All are compounds described in JP-A-61-201247) It is clear that when the compounds of the present invention are used, the levels are practically problem-free.

Example 3 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material having the following composition was prepared and used as Sample 301.

1st layer: Anti-halation layer Black colloidal silver 0.25g / m ² UV absorber U-1 0.04g / m ² UV absorber U-2 0.1g / m ² UV absorber U-3 0.1g / m ² High boiling point Organic solvent Oil-2 Gelatin layer containing 0.01 CC / m ² (dry film thickness 2 μ) Second layer: Intermediate layer Compound Cpd C 0.05 g / m ² Compound I-1 0.05 g / m ² High boiling organic solvent Oil-1 Gelatin layer containing 0.05 CC / m ² (dry film thickness 1 μm) Third layer: first red emulsion layer Silver bromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.3 μ AgI content 4 mol%) Silver amount ... 0.5 g / m ² coupler F-1 0.2 g / m ² coupler F-2 0.05 g / m ² compound I-2 2 × 10 ⁻³ g / m ² high boiling organic solvent Oil-1 Gelatin layer containing 0.12 CC / m ² (dry film thickness 1 μm) Fourth layer: second red-sensitive emulsion layer Silver bromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average) Particle size: 0.6μ, AgI content: 3 mol%) Silver amount: 0.8g / m ² coupler F-1 0.5 5 g / m ² coupler F-2 0.14 g / m ² compound I-2 1 × 10 ⁻³ g / m ² high boiling point organic solvent Oil-1 0.33 CC / m ² dye D-1 0.02 g / m ² containing gelatin Layer (dry film thickness 1.5 μ) Fifth layer: intermediate layer Compound Cpd C 0.1 g / m ² High boiling point organic solvent Oil-1 0.1 CC / m ² Dye D-2 0.02 g / m ² Gelatin layer containing dry film (dry film) Thickness 1 μ) Sixth layer: First green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (average grain size 0.3 μm, AgI content 4 mol%) Silver amount ... 0.7 g / m ² coupler F-3 0.20 g / m ² coupler F-5 0.10 g / m ² gelatin layer containing high boiling organic solvent Oil-1 0.26 CC / m ² (dry film thickness 1 μm) 7th layer: second green feeling Emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (average grain size: 0.6 μm, AgI content: 2.5 mol%) Silver amount: 0.7 g / m ² Coupler F-4: 0.10 g / m ² gelatin containing coupler F-5 0.10g / m ² high-boiling organic solvent ^Oil-2 0.05CC / m 2 dye D-3 0.05g / m ² Layer (dry film thickness 2.5 [mu]) 8th layer: Gelatin layer containing an intermediate layer Compound Cpd C 0.05g / m ² High-boiling organic solvent ^Oil-2 0.1CC / m 2 Dye D-4 0.01g / m ² (dry film Thickness 1 μ) Ninth layer: Yellow filter layer Yellow colloidal silver 0.1 g / m ² compound Cpd C 0.02 g / m ² compound Cpd B (same as Example 0.03 g / m ² 1) High boiling organic solvent Oil-1 0.04CC / m ² containing gelatin layer (dry film thickness 1 μm) 10th layer: first blue-sensitive emulsion layer Tabular silver iodobromide emulsion containing sensitizing dye S-5 (average aspect ratio 8, average grain size 0.7 μm, AgI content 2 mol%) Silver amount ... 0.6 g / m ² coupler F-6 0.1 g / m ² coupler F-7 0.4 g / m ² Gelatin layer containing high boiling organic solvent Oil-1 0.1 CC / m ² (dry) Film thickness 1.5 μ) 11th layer: 2nd blue-sensitive emulsion layer A tabular silver iodobromide emulsion containing sensitizing dye S-6 (average aspect ratio 12, average grain size 1.2 μm, AgI content 2 mol%) silver amount ... 1.1g / m ² coupler F-6 0.4g / m ² coupler -8 0.8 g / m ² gelatin layer containing a high-boiling organic solvent Oil-1 0.23CC / m ² Dye D-5 0.02g / m ² (dry thickness 3.mu.) 12th layer: 1st protective layer ultraviolet absorber U -1 0.02 g / m ² UV absorber ^U-2 0.32g / m 2 UV absorber U-3 0.03g / m ² gelatin layer containing a high-boiling organic solvent ^Oil-2 0.28CC / m 2 (dry thickness 2μ ) Thirteenth layer: Second protective layer Surface-fogged fine grain silver iodobromide emulsion Silver amount: 0.1 g / m ² (iodine content 1 mol%, average grain size 0.06 μ) Polymethylmethacrylate grains (average grain size 1.5 gelatin layer (dry film thickness 2.5 μ) In addition to the above composition, a gelatin hardening agent H-1 (same as in Example 1) and a surfactant were added to each layer.

The compounds used to make the samples are shown below.

The high boiling point organic solvents Oil-1 and Oil-2 are the same as those used in Example 1.

Preparation of Samples 302 to 310 Coupler F- in the third and fourth layers of Sample 301
It was prepared in the same manner as in Sample 301 except that the couplers shown in Table 3 were replaced by equimolar amounts of 1 and F-2.

The sample prepared as described above was subjected to a running test by the following process in the same manner as in Example 1, and in this case, the amount of residual silver in the unexposed portion was measured. The results are shown in Table 3.

The method of replenishing the washing bath here is to put the replenisher into the washing bath,
The so-called countercurrent replenishment system was used to guide the overflow of washing with water.

Also, bleach overflow led to bleach-fix.

The composition of the treatment liquid was as follows.

Adjust the pH with hydrochloric acid or potassium hydroxide.

First rinse solution (both tank solution and replenisher solution) First rinse solution 0 solution KH ₂ PO ₄ 6.0 g 5-Sulfosalicylic acid 1.5 g Water added 1000 ml pH 7.0 Inversion solution (both tank solution and replenisher solution) Nitrilo-N , N, N-Trimethylenephosphonic acid pentasodium salt 3.0g Stannous chloride (dihydrate) 1.0g p-Aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add ice 1000ml pH 6.0 pH is hydrochloric acid or Adjust with sodium hydroxide.

Adjust the pH with hydrochloric acid or sodium hydroxide.

Stabilizer Water 800 ml Formalin (37%) 5.0 ml Fuji Drywell 5.0 ml Add water to 1000 ml As is clear from the above table, the residual silver amount in the sample of the present invention is practically acceptable.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion layer and a bleach accelerator releasing coupler, wherein the bleach accelerator releasing coupler is represented by the following general formula (I). A characteristic silver halide photographic light-sensitive material. General formula (I) In the formula, A represents a coupler mother nucleus, TIME represents a timing group, n represents 0 or 1, R represents a trivalent aliphatic group having 8 or less carbon atoms, and X represents —OH, —CO ₂ M. , -SO ₃ M or Represents Y, -SO ₃ M, Or represents -OR ₅ . Here, M represents a cation or a hydrogen atom, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or an aliphatic group having 8 or less carbon atoms or a phenyl group, and R ₅ represents fat having 8 or less carbon atoms. Represents a group or phenyl group. 2. A silver halide photographic light-sensitive material containing a silver halide photographic emulsion layer and a bleaching accelerator-releasing coupler represented by the following general formula (I) is subjected to color development in a bleach-fixing bath without washing with water. A method for processing a silver halide photographic light-sensitive material, characterized in that General formula (I) In the formula, A represents a coupler mother nucleus, TIME represents a timing group, n represents 0 or 1, R represents a trivalent aliphatic group having 8 or less carbon atoms, and X represents —OH, —CO ₂ M. , -SO ₃ M or Represents Y, -SO ₃ M, Or represents -OR ₅ . Here, M represents a cation or a hydrogen atom, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or an aliphatic group having 8 or less carbon atoms or a phenyl group, and R ₅ represents fat having 8 or less carbon atoms. Represents a group or phenyl group.