JPH0715566B2 - 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. 1144.
9 and JP-A-61-2201247.

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 development 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 disulphide body, but it is difficult to identify either. It is known that thiol produces disulphide by air oxidation etc. (especially fast in alkaline solution), (Nihon Kagaku ed., "New Experimental Chemistry Course, Vol. 14," p1735, Maruzen (1978)). It is speculated that some of them are disulphides.

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 Pr
It is described in ess (1966). Therefore, as described above, the deterioration of the bleaching-promoting effect in the running state means that the sulfite ion brought from the developing solution into the bleaching solution turns the thiol or disulfide into a thiol sulfonate ion, which causes It is considered that the cause is that the adsorption force is weakened.

Therefore, these known bleach accelerating agent 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.

Secondly, it is to provide a processing method of a silver halide color photographic light-sensitive material capable of achieving a rapid silver bleaching speed and a rapid processing.

The above object is 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). And a silver halide photographic light-sensitive material.

In the general formula (I) A- (TIME) _n -SR _1- (XR ₂ ) _m- (Y) _l , A represents a coupler nucleus, TIME represents a timing group, n represents 0 or 1, and R ₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, Y is an oxygen atom, a sulfur atom, Represents —OSO ₂ — or —SO ₂ O—, and R ₂ has 1 to 8 carbon atoms.
Represents a divalent aliphatic group, m represents an integer of 1 to 3, and when m is a plural number, m X-R ₂ represent the same or different, and Y represents -OH, -CO ₂ M, −SO ₃ M, or And 1 represents 1 to 3, and when 1 is plural, 1 Y represents the same or different. Here, M represents a cation or a hydrogen atom, and R ₃ and R ₄ each represent a hydrogen atom or an aliphatic group having 6 or less carbon atoms.

The aliphatic group represented by R ₁ and R ₂ may be saturated or unsaturated, linear or cyclic, linear or branched.

The aliphatic group represented by R ₃ and R ₄ may be saturated or unsaturated, linear or cyclic, linear or branched.

The following are typical examples.

R ₁ is --CH ₂ CH ₂ -,-(CH ₂ ) _3- , --CH ₂ -,-(CH ₂ )
_4- , And so on.

For R _{2 -CH 2 -, - CH 2 -CH} 2 -, - (CH 2) 3 -, - (CH 2) 4 -, And so on.

R ₃ and R ₄ are a methyl group, an ethyl group, a propyl group,
Examples include isopropyl group.

Examples of M include a hydrogen atom, sodium ion, potassium ion, pyridinium ion, ammonium ion and the like.

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),
A more preferred example is a coupler residue represented by (Cp-7), (Cp-8) or (Cp-9). 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 ₆₃ contains a diffusion resistant group, it is selected to have a total number of carbon atoms of 8 to 40, preferably 10 to 30, otherwise the total number of carbon atoms is 15 The following are preferred. 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.

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 or an aromatic group. Represents a group or a complex waterfall 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 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-5-yl group, 2,4-dioxo-1,3-imidazolidin-3-yl 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, And a -group, a cyano group or a nitro group. Where R
₄₆ represents an aliphatic group, an aromatic group, or a heterocyclic group, 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, 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 as R ₄₁ OCONH
-Group, R ₄₁ CONH-group, or 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 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- group
A 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, 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
-Tetramethylbutyl) phenylsulfonamido} ethyl group or dodecylthio group. R ₅₈ is a 2-chlorophenyl group, a 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 Groups. R ₅₉ is a chloro atom, a methyl group, an ethyl group, a propyl group, a butyl group,
Isopropyl group, 2- (2,4-di-t-amylphenoxy) butanamide group, 2- (2,4-di-t-amylphenoxy) hexanamide group, 2- (2,4-di-t-octylphenoxy) Si) octanamide group, 2- (chlorophenoxy) tetradecanamide group, 2,2-dimethylpropanamide group, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} tetradecanamide group, or 2
And a-{2- (2,4-di-t-amylphenoxyacetamido) phenoxy} butanamide group. R ₆₀ is a 4-cyanophenyl group, a 2-cyanophenyl group,
4-butylsulfonylphenyl group, 4-propylsulfonylphenyl group, 4-ethoxycarbonylphenyl group,
4-N, N-diethylsulfamoylphenyl group, 3,4-dichlorophenyl group or 3-methoxycarbonylphenyl group can be mentioned. As R ₆₁ , 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) phenyl group, 2-methoxy-5-dodecyloxycarbonylphenyl group, 2-butoxyphenyl group or 1-naphthyl group. R ₆₂ is an isobutyloxycarbonylamino group, an ethoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfoamide group, a butanesulfonamide group, a 4-methylbenzenesulfonamide group, a benzamide group, a trifluoroacetamide group, 3
-Phenylureido group, butoxycarbonylamino group,
Alternatively, an acetamide group may be mentioned. R ₆₃ is 2,4
-Di-t-amylphenoxyacetamide group, 2- (2,
4-di-t-amylphenoxy) butanamide group, hexadecylsulfonamide group, N-methyl-N-octadecylsulfamoyl group, N, N-dioctylsulfamoyl group, dodecyloxycarbonyl group, chlor atom, fusoso atom, Nitro group, cyano group, N-3- (2,4-di-
Examples thereof include t-amylphenoxy) propylsulfamoyl group, methanesulfonyl group and hexadecylsulfonyl group.

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
Is a substituent and a representative example of ₆₇ is 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, E represents an electrophilic group, and a bond with ** is cleaved by a nucleophilic attack from Nu. Link is a group that can form a sterically related linking group such that Nu and E 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 described in U.S. Pat. No. 4,409,323 or 4,421,845 and is represented by the following general formula.

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 compound of the present invention can be synthesized by a known method. For example, U.S. Patent Nos. 4,293,691 and 4,264,723, JP-A-61
-201247 or 55-29805, and the like.

Synthesis Example (Synthesis of Compound (1)) The compound was synthesized by the following reaction.

49.3 g of the compound (i), 21.5 g of the compound (ii) and 15 g of triethylamine were mixed with 250 ml of tetrahydrofuran and reacted at room temperature under a nitrogen atmosphere for 2 hours. After the post-treatment, the product was recrystallized with a mixed solvent of dichloromethane and hexane to obtain 38.2 g of the desired exemplified compound (1).

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% of the total coated silver amount,
It is preferably 0.1 mol% to 50 mol%, particularly preferably 1 mol%.
Mol% to 20 mol%.

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] Here, Y ′ represents NH, CO or SO ₂ , q is zero or 1, R ₁₈ is a hydrogen atom, a fatty acid 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 R is a plural number, a plurality of R ₂₄ may be the same or different. As preferable substituents, R ₂₂ and R ₂₃ are linear or branched alkyl groups having 1 to 18 carbon atoms,
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 30, 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. Ar has 6 to 30 carbon atoms, 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
Aliphatic group, aromatic group having 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, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert-amylphenoxypropyl group, 2,4-di-tert
-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, vinylacetophenone and sulfostyrene), itaconic acid,
Examples include citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and -4-vinyl pyridine.

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 Zelikmann et al., VLZelikman et al, Making and Coating Photograp
hic 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
It can be easily prepared by the method described in Japanese 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 Nos. 17643 and No. 18716, and the relevant parts are summarized in the following labels.

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, 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,
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, for example, 427,767 and European Patent 161,626A 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 US Pat. No. 4,130,427, US Pat. Nos. 4,283,472, and 4,338,393.
Multi-equivalent couplers described in Japanese Patent No. 4,310,618 and the like, JP-A-60-
Examples thereof include DIR redox compound releasing couplers described in 185950 and the like, couplers releasing a dye that restores color after separation described in EP 173,302A, and the like.

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 bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Technology" edited by the Society for Hygiene Technology, "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Society for Antibacterial and Antifungal Society of Japan.

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.

The stabilizing bath refers to a bath having an image stabilizing function that cannot be obtained by the rinse bath in addition to the function as the rinse bath, and corresponds to, for example, a bath containing formalin. In addition, the carry-in amount from the pre-bath means the volume of the pre-bath adhering to and absorbed by the light-sensitive material and mixed in the rinse bath. The color light-sensitive material collected immediately before entering the rinse bath is immersed in water. It can be calculated by extracting the component and measuring the amount of the pre-bath component in the extract.

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 represented by trichlorophenol, or promophenol compounds, or organotin organozinc compounds, or thiocyanate or isothiocyanate compounds, Alternatively,
Acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole alkylguanidine compounds, quaternary ammonium salts such as benzalkonium chloride, or penicillin. Antibiotics, such as JANANTI BACTERIA AND ANTIHUANGUS AGENT (J.Antibact.Antifung.
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. Furthermore, 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.
Product names such as 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. If the pressure is 20 kg / cm 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 …… 5 × 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 methacrylate particles (diameter 1.5μ) …… 0.2
g / m ² Hardener H-1 …… 0.4g / m ² Formaldehyde scavenger-S-1 0.5g / m ² Formaldehyde scavenger-S-2 …… 0.5g / m ² In addition to the ingredients, a surfactant was added 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 Tricresyl 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 mother liquor and replenisher 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 In addition, 1 <Rinsing water> As washing water, tap water was passed through a column filled with a Na-type strongly acidic cation exchange resin (Diaion SK-1B manufactured by Mitsubishi Kasei Co., Ltd.) to obtain calcium 2 mg / l and magnesium. 1.2
The water quality of mg / 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 ml / 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 disodium salt was added.

pH 6.7 It was carried out by the steps and treatment solutions 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 µ) 0.2 Formaldehyde scavenger-H-10.5 In addition, surfactant W-1 and hardener H-1 were added.

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

Samples 211 to 220 Samples 211 to 220 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 μAgI 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 −12 Gelatin layer containing 0.2 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 grain diameter a 0.6 micron, AgI content 3 mol%) silver ... 0.8 g / m ² coupler F-1 0.55g / m ² Ca Puller F-2 0.14 g / m ² compound I-2 1 × 10 ⁻³ g / m ² Gelatin layer containing high boiling point organic solvent Oil-1 0.33 CC / m ² (dry film thickness 2.5 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 containing gelatin layer (dry film thickness 1 μ) 6th layer: 1st green 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 μ) 7th layer: second green emulsion layer Sensitizing dyes S-3 and S-4 Silver iodobromide emulsion (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 coupler F-5 0.10 g / m ² high boiling organic solvent Oil-2 0.05CC / m ² Dye D-3 0.05g / m ² containing gelatin layer (dry film thickness 2.5μ) 8th layer : Intermediate layer Compound Cpd C 0.05 / m ² High boiling point organic solvent Oil-2 0.1CC / m ² Dye D-4 Gelatin layer containing 0.01 g / m ² (dry film thickness 1 μm) 9th layer: Yellow filter layer Yellow colloid Silver 0.1 g / m ² compound Cpd C 0.02 g / m ² compound Cpd B (same as in Example 1) 0.03 g / m ² Gelatin layer containing high boiling organic solvent Oil-1 0.04 CC / m ² (dry film thickness 1 μm ) Tenth layer: first blue-sensitive emulsion layer A 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 0.1g / m ² coupler F-7 0.4g / m ² gelatin layer containing high boiling point organic solvent Oil-1 0.1CC / m ² (dry film thickness 1.5μ) 11th layer: 2nd blue Emulsion Sensitive 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 ... 1.1 g / m ² coupler F-6 0.4 g / m ² Coupler F-8 0.8g / m ² High boiling organic solvent Oi l-1 0.23 CC / m ² dye D-5 Gelatin layer containing 0.02 g / m ² (dry film thickness 3 μm) 12th layer: first protective layer UV absorber U-1 0.02 g / m ² UV absorber U -2 0.32 g / m ² UV absorber U-2 0.03 g / m ² high-boiling organic solvent Oil-2 0.28 cc / m gelatin layer containing ² (dry film thickness 2.mu.) 13 layer: the second protective layer surface Fogging fine grain silver iodobromide emulsion Silver amount: 0.1 g / m ² (iodine content 1 mol%, average particle size 0.06μ) Gelatin layer containing polymethylmethacrylate particles (average particle size 1.5μ) (dry film thickness 2.5 μ) In addition to the above composition, gelatin hardening agent H-1 (the 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, the overflow of the bleaching solution led to the bleach-fixing solution.

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. In the general formula (I) A- (TIME) _n -SR _1- (XR ₂ ) _m- (Y) _l , A represents a coupler nucleus, TIME represents a timing group, and n represents 0 or 1. , R ₁ has 1 to 8 carbon atoms
Represents a divalent aliphatic group of, X is an oxygen atom, a sulfur atom, Represents —OSO ₂ — or —SO ₂ O—, and R ₂ has 1 to 8 carbon atoms.
Represents a divalent aliphatic group, m represents an integer of 1 to 3, and when m is plural, a plurality of X—R ₂ represent the same or different, and Y represents —OH, —CO ₂ M. , -SO ₃ M, or And 1 represents 1 to 3, and when 1 is plural, plural Y's represent the same or different, wherein M represents a cation or a hydrogen atom, and R ₃ and R ₄ represent a hydrogen atom or It represents an aliphatic group having 6 or less carbon atoms. 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 In the general formula (I) A- (TIME) _n -SR _1- (XR ₂ ) _m- (Y) _l , A represents a coupler nucleus, TIME represents a timing group, and n represents 0 or 1. , R ₁ has 1 to 8 carbon atoms
Represents a divalent aliphatic group of, X is an oxygen atom, a sulfur atom, Represents —OSO ₂ — or —SO ₂ O—, and R ₂ has 1 to 8 carbon atoms.
Represents a divalent aliphatic group, m represents an integer of 1 to 3, and when m is plural, a plurality of X—R ₂ represent the same or different, and Y represents —OH, —CO ₂ M. , -SO ₃ M, or And 1 represents 1 to 3, and when 1 is plural, plural Y's represent the same or different, wherein M represents a cation or a hydrogen atom, and R ₃ and R ₄ represent a hydrogen atom or It represents an aliphatic group having 6 or less carbon atoms.