JP2534884B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photographic light-sensitive material containing a novel compound capable of making a photographically useful group available during development.

(Prior Art) With respect to the color-reducing color photographic light-sensitive material, a lot of research has been conducted for the purpose of improving sharpness, improving graininess, improving color reproducibility, improving desilvering property or increasing sensitivity. Came.

One such technique is the use of couplers that release photographic useful groups. Representative examples of the photographically useful group are a development inhibitor, a bleaching accelerator, a dye, a fogging agent and a developing agent. In addition to the coupler that cleaves the photographic utilization group from the coupling position of the coupler, recently, from the coupling position,
Couplers that release couplers that cleave a photographically useful group are disclosed.

For example, JP-A-60-203943, 62-291645, and 60-
The couplers described in 185950 or 60-213944 are known.

In addition to the above group of couplers, a group of compounds capable of releasing a photographically useful group through an oxidation-reduction reaction have been conventionally known.

For example, as a hydroquinone derivative releasing a development inhibitor, U.S. Patent No. 4,144,071, U.S. Patent No. 4,377 ,,
Examples thereof include compounds described in US Pat. No. 634, US Pat. No. 4,332,878 and the like.

Compounds described in US Pat. No. 4,459,351 are known as hydroquinone derivatives which release silver halide solvents.

Although these known compounds have a certain level of performance, further improvements have been desired.

(Problems to be Solved by the Invention) An object of the present invention is to provide a color photographic light-sensitive material having improved sharpness, improved graininess, improved color reproducibility, improved desilvering property or high sensitivity. is there.

(Means for Solving Problems) The above object was achieved by a silver halide photographic light-sensitive material characterized by containing at least one compound represented by the following general formula (I).

(In the formula, A represents a group in which a bond with a residue other than A is cleaved by reacting with an oxidized product of a developing agent, and L is a bond with a residue except L after the bond with A is cleaved. Represents a group which is cleaved, and X is And R represents an organic residue for constituting a 5-membered nitrogen-containing heterocycle described below, R represents a hydrogen atom, a substituent or PUG, PUG represents a photographically useful group, and a represents 0 or 1
Represents ) The reaction process in which the compound of the present invention releases PUG during development is presumed as follows.

 Where T Represents an oxidized product of a developing agent, and A, L, a,
X, R and PUG are the same as those described in the general formula (I).
Have the same meaning. From the above scheme, the compound of the present invention
The features are understood. That is, in the compound of the present invention, PUG
Release rate of PUG and reach of PUG
Of the intermediate compound (ii) or (iii) Against
Affected by response speed. Their regulation is in PUG
It can be easily performed according to each purpose.

The compound represented by the intermediate compound (ii) or (iii) is a kind of DIR coupler (development inhibitor releasing coupler) when PUG is a development inhibitor, for example, JP-A-52-8242.
It is described in No. 3.

The group represented by A in the general formula (I) is a coupler residue or a redox group.

When A represents a coupler residue, for example, a yellow coupler residue (eg, an open-chain ketomethylene-type coupler residue),
Magenta coupler residue (for example, 5-pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type, etc. coupler residue), cyan coupler residue (for example, phenol type, naphthol type, etc. coupler residue), and achromatic coupler Examples thereof include residues (for example, indanone type and acetophenone type coupler residues). In addition, US patent
4,315,070, 4,183,752, 4,174,969, 3,96
It may be a heterocyclic coupler residue described in No. 1,959 or No. 4,171,223.

When A represents a coupler residue in the general formula (I), the following general formulas (Cp-1), (Cp-2), (Cp-3),
(Cp-4), (Cp-5), (Cp-6), (Cp-7),
A more preferred example is a coupler residue represented by (Cp-8) or (Cp-9). These couplers are preferred because of their high coupling speed.

In the above formula, the free bond in the general formula (I) is Represents the binding position of.

In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R
_{When 58} , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ , or R ₆₃ contains a diffusion resistant group, it has a total carbon number of 8 to 40, preferably 10
To 30 and otherwise the total number of carbons is preferably below 15. 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 hetero group, R ₄₃ , R
₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ are each R
_{Has the} same meaning as ₄₂ . R ₅₄ has the same meaning as R ₄₁ , R ₄₁ S- group, R ₄₃ O group, R ₄₁ OOC-group, Or an N = C- group. R ₅₅ represents a group having the same meaning as R ₄₁ . R ₅₆ and R ₅₇ each have 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 ₄₇ . 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 a divalent group and connected to each other 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 is a saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
As typical examples, methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl, (i) -butyl,
(T) -Amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

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

The heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, and is selected as a hetero atom from a nitrogen atom, an oxygen atom or a sulfur atom. It is preferably a substituted or unsubstituted heterocyclic group having a 3- to 8-membered ring. Typical examples of the heterocyclic group are 2-pyridyl, 4-pyridyl, 2-thienyl, 2-
Furyl, 2-imidazolyl, pyrazinyl, 2-pyrimidinyl, 1-imidazolyl, 1-indolyl, phthalimido, 1,3,4-thiadiazol-2-yl, benzoxazol-2-yl, 2-quinolyl, 2,4-dioxo -1,3
-Imidazolidin-5-yl, 2,4-dioxo-1,3-imidazolidin-3-yl, succinimide, phthalimido, 1,2,4-triazol-2-yl or 1-pyrazolyl.

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

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

R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ , R ₅₃
And R ₅₅ is preferably an aromatic group. R ₅₄ is R ₄₁ CONH- group,
Or Is preferred. R ₅₆ and R ₅₇ are preferably an aliphatic group, R ₄₁ O— group, or R ₄₁ S— group. R ₅₈ is preferably an aliphatic group or an aromatic group. In formula (Cp-6), R ₅₉ is preferably a chlorine 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 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 is R ₄₁ CONH- group, R ₄₁ SO ₂ NH- group, R ₄₁ SO ₂ — group, A nitro group or a cyano group is preferred.

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

Examples of R ₅₁ include (t) -butyl, 4-methoxyphenyl, phenyl, 3- {2- (2,4-di-t-amylphenoxy) butanamide} phenyl, 4-octadecyloxyphenyl or methyl. R ₅₂ and R ₅₃
Is 2-chloro-5-dodecyloxycarbonylphenyl, 2-chloro-5-hexadecylsulfonamidophenyl, 2-chloro-5-tetradecanoamidophenyl, 2-chloro-5- {4- (2,4-diphenyl). -T-amylphenoxy) butanamide} phenyl, 2-chloro-5-
{2- (2,4-di-t-amylphenoxy) butanamide} phenyl, 2-methoxyphenyl, 2-methoxy-
5-tetradecyloxycarbonylphenyl, 2-chloro-5- (1-ethoxycarbonylethoxycarbonyl) phenyl, 2-pyridyl, 2-chloro-5-octyloxycarbonylphenyl, 2,4-dichlorophenyl, 2-chloro-5 Examples include-(1-dodecyloxycarbonylethoxycarbonyl) phenyl, 2-chlorophenyl or 2-ethoxyphenyl.

R ₅₄ is 3- {2- (2,4-di-t-amylphenoxy) butanamide} benzamide, 3- {4- (2,
4-di-t-amylphenoxy) butanamide} benzamide, 2-chloro-5-tetradecanamide anilino, 5- (2,4-di-t-amylphenoxyacetamide) benzamide, 2-chloro-5-dodecene Nylsuccinimidoanilino, 2-chloro-5- {2- (3-t-
Butyl-4-hydroxyphenoxy) tetradecanoamide} anilino, 2,2-dimethylpropanamide, 2-
Mention may be made of (3-pentadecylphenoxy) butanamide, pyrrolidino or N, N-dibutylamino. R ₅₅ includes 2,4,6-trichlorophenyl, 2-chlorophenyl, 2,5-dichlorophenyl, 2,3-dichlorophenyl,
2,6-dichloro-4-methoxyphenyl, 4- {2-
(2,4-Di-t-amylphenoxy) butanamide} phenyl or 2,6-dichloro-4-methanesulfonylphenyl are preferred examples. R ₅₆ is methyl, ethyl, isopropyl, methoxy, ethoxy, methylthio,
Mention may be made of ethylthio, 3-phenylureido, 3-butylureido, or 3- (2,4-di-t-amylphenoxy) propyl. R ₅₇ is 3- (2,4-di-t-
Amylphenoxy) propyl, 3- [4- {2- [4-
(4-Hydroxyphenylsulfonyl) phenoxy] tetradecanamido} phenyl] propyl, methoxy, ethoxy, methylthio, ethylthio, methyl, 1-methyl-2- {2-octyloxy-5- [2-octyloxy-5- (1 , 1,3,3-Tetramethylbutyl) phenylsulfonamido] phenylsulfonamido} ethyl, 3-
{4- (4-dodecyloxyphenyl sulfonamide)
Phenyl} propyl, 1,1-dimethyl-2- {2-octyloxy-5- (1,1,3,3-tetramethylbutyl) phenylsulfonamido} ethyl, or dodecylthio. R ₅₈ is 2-chlorophenyl, pentafluorophenyl, heptafluoropropyl, 1- (2,
4-di-t-amylphenoxy) propyl, 3- (2,4-
Di-t-amylphenoxy) propyl, 2,4-di-t-
Amylmethyl or furyl may be mentioned. R ₅₉ is a chlorine atom, methyl, ethyl, propyl, butyl, isopropyl, 2- (2,4-di-t-amylphenoxy) butanamide, 2- (2,4-di-t-amylphenoxy)
Hexanamide, 2- (2,4-di-t-octylphenoxy) octanamide, 2- (2-chlorophenoxy)
Tetradecane amide, 2,2-dimethylpropanamide,
2- {4- (4-hydroxyphenylsulfonyl) phenoxy} tetradecanamide, or 2- {2- (2,4
-Di-t-amylphenoxyacetamide) phenoxy} butanamide. R ₆₀ is 4-cyanophenyl, 2-cyanophenyl, 4-butylsulfonylphenyl, 4-propylsulfonylphenyl, 4-ethoxycarbonylphenyl, 4-N, N-diethylsulfamoylphenyl, 3,4-dichlorophenyl or 3-
Methoxycarbonylphenyl may be mentioned. R ₆₁ includes dodecyl, hexadecyl, cyclohexyl, butyl,
3- (2,4-di-t-amylphenoxy) propyl, 4
-(2,4-di-t-amylphenoxy) butyl, 3-dodecyloxypropyl, 2-tetradecyloxyphenyl, t-butyl, 2- (2-hexyldecyloxy) phenyl, 2-methoxy-5-dodecyl Oxycarbonylphenyl, 2-butoxyphenyl or 1-naphthyl may be mentioned. Examples of R ₆₂ include isobutyloxycarbonylamino, ethoxycarbonylamino, phenylsulfonylamino, methanesulfonamide, butanesulfonamide, 4-methylbenzenesulfonamide, benzamide, trifluoroacetamide, 3-phenylureido, butoxycarbonylamino or acetamide. To be R ₆₃ includes 2,4-di-t-amylphenoxyacetamide, 2- (2,4-di-t-amylphenoxy) butanamide, hexadecylsulfonamide, N-
Methyl-N-octadecylsulfamoyl, N, N-dioctylsulfamoyl, dodecyloxycarbonyl, chlorine atom, fluorine atom, nitro group, cyano group, N-3 (2,
4-di-t-amylphenoxy) propylsulfamoyl, methanesulfonyl or hexadecylsulfonyl.

When A represents a redox group in the general formula (I),
The general formula (I) is specifically represented by the following general formula (R-1).

In the formula, L, X, R, PUG and a have the same meanings as described in the general formula (I), P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and n At least one of Z and Y in (L) _a represents a methine group bonded to (a), the other Z and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n represents an integer of 1 to 3 ( n number of Z, n
Y's represent the same or different), A ₁ and A ₂ each represent a hydrogen atom or a group removable by an alkali. Where P, Z, Y, Q, A ₁ and A ₂
It also includes the case where any two of the above substituents are combined into a divalent group to form a cyclic structure. For example, (Z = Y) _n forms a benzene ring, a pyridine ring, or the like.

When P and Q represent a substituted or unsubstituted imino group, it is preferably an imino group substituted with a sulfonyl group.

 At this time, P and Q are expressed as follows.

Here, the * mark represents the position at which it binds to A ₁ or A _2, and *
The * mark represents the position at which one of the free bonds of-(Z = Y _n is bonded.

In the formula, the group represented by G is a linear or branched, chained or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32 carbon atoms, preferably 1 to 22 (eg, methyl,
Ethyl, benzyl, phenoxybutyl, isopropyl), a substituted or unsubstituted aromatic group having 1 to 10 carbon atoms (eg, phenyl, 4-methylphenyl, 1-naphthyl, 4
-Dodecyloctylphenyl) or a hetero atom selected from a nitrogen atom, a sulfur atom or an oxygen atom 4
Membered to 7-membered heterocyclic groups (eg 2-pyridyl, 1-
Phenyl-4-imidazolyl, 2-furyl, benzothienyl) are preferred examples.

A group in which A ₁ and A ₂ can be removed by an alkali (hereinafter,
When referred to as a precursor group), preferably a hydrolyzable group such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxazolyl group and a sulfonyl group, the reverse described in U.S. Patent No. 4,009,029. Precursor group of the type utilizing the Michael reaction, a type of precursor group utilizing the anion generated after the ring opening reaction described in U.S. Pat.No. 4,310,612 as an intramolecular nucleophilic group, U.S. Pat.No. 3,674,478,
Anion described in 3,932,480 or 3,993,661 undergoes electron transfer through a conjugated system, thereby causing a cleavage reaction, a precursor group, a cleavage reaction by electron transfer of the anion reacted after ring cleavage described in U.S. Pat.No. 4,335,200. Precursor base or U.S. Pat. No. 4,363,86
Precursor groups utilizing an imidomethyl group described in No. 5 and No. 4,410,618 are mentioned.

Preferably in general formula (R-1) P is an oxygen atom, is when A ₂ represents a hydrogen atom.

More preferably, in the general formula (R-1), Z or Y is a substituted or unsubstituted methine group, except when Z or Y is a methine group bonded to L.

Among the compounds represented by the general formula (R-1), particularly preferable compounds are represented by the following general formula (R-2) or (R-3).

In the formula, L, PUG, R, X, a, P, Q, A ₁ and A ₂ have the same meanings as described in the general formula (R-1), R ₁ represents a substituent, and q represents Represents an integer of 1 to 3. When q is 2 or more, two or more R _1's may be the same or different, and when two R _1's are substituents on adjacent carbons, they are each a divalent group and are linked to each other to represent a cyclic structure. It also includes cases. At that time, it becomes a benzene condensed ring, for example, naphthalene, benzonorbornenes, chromanes, indoles, benzothiophenes, quinolines, benzofurans, 2,3-dihydrobenzofurans,
It becomes a ring structure such as indans or indenes, which may further have one or more substituents. Examples of preferred substituents when having this fused ring substituents, and preferred examples of R ₁ when R ₁ does not form a condensed ring are those listed below. That is, an aliphatic group (eg, methyl, ethyl, allyl, benzyl, dodecyl), an aromatic group (eg, phenyl, naphthyl, 4-phenoxycarbonylphenyl), a halogen atom (eg, chlorine atom, bromine atom), an alkoxy group (eg, methoxy). , Hexadecyloxy), alkylthio groups (eg methylthio, dodecylthio, benzylthio), aryloxy groups (eg phenoxy, 4-t-octylphenoxy, 2,4-di-
t-amylphenoxy), an arylthio group (eg phenylthio, 4-dodecyloxyphenylthio), a carbamoyl group (eg N-ethylcarbamoyl, N-hexadecylcarbamoyl, N-3- (2,4-di-t-amylphenoxy). ) Propylcarbamoyl, N-methyl-N-
Octadecylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, 2-cyanoethoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl, 3- (2,4-di-t-amylphenoxy) propoxycarbonyl), an aryloxycarbonyl group (eg, phenoxy). Carbonyl, 4-nonylphenoxycarbonyl), sulfonyl group (eg methanesulfonyl, benzenesulfonyl, p-toluenesulfonyl), sulfamoyl group (eg N-propylsulfamoyl, N-methyl-N-octadecylsulfamoyl, N-phenyl). Sulfamoyl, N-dodecylsulfamoyl), an acylamino group (eg acetamide, benzamide, tetradecanamide, 4- (2,4-di-t-amylphenoxy) butanamide, 2- 2,4-di -t- amylphenoxy) butanamide, 2- (2,4-di -t- amylphenoxy) tetradecanamido), a sulfonamido group (e.g., methanesulfonamido, benzenesulfonamide,
Hexadecyl sulfonamide), acyl group (eg acetyl, benzoyl, myristoyl, palmitoyl), nitroso group, acyloxy group (eg acetoxy, benzoyloxy, lauryloxy), ureido group (eg 3
-Phenylureido, 3- (4-cyanophenylureido), nitro group, cyano group, heterocyclic group (4 selected from nitrogen atom, oxygen atom or sulfur atom as a hetero atom)
Membered to 6-membered heterocyclic group, for example, 2-furyl group, 2-
Pyridyl, 1-imidazolyl, 1-morpholino), hydroxyl group, carboxyl group, alkoxycarbonylamino group (eg methoxycarbonylamino), phenoxycarbonylamino, dodecyloxycarbonylamino), sulfo group, amino group, arylamino group (eg anilino) , 4-methoxycarbonylanilino), an aliphatic amino group (eg, N, N-diethylamino, dodecylamino), a sulfinyl group (eg, benzenesulfinyl,
Propylsulfinyl), sulfamoylamino group (eg 3-phenylsulfamoylamino), thioacyl group (eg thiobenzoyl), thioureido group (eg 3-phenylthioureido), heterocyclic thio group (eg thiadiazolylthio). , An imide group (for example, succinimide, phthalimide, octadecenylimide) or a heterocyclic amino group (for example, 4-imidazolylamino, 4-pyridylamino) and the like.

When there is an aliphatic group moiety in the partial structure of the above substituent,
It has 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, and is a linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group.

When the partial structure of the above-mentioned substituent has an aromatic group, it has 6 to 10 carbon atoms, and preferably a substituted or unsubstituted phenyl group. In the general formula (I), A is preferably a coupler residue.

The group represented by L in the general formula (I) may or may not be used in the present invention. Not used (a = 0)
Although more preferable, when used, examples thereof include the following known linking groups or timing groups.

(1) Group Utilizing Cleavage Reaction of Hemiacetal For example, the group is described in U.S. Pat. No. 4,146,396, JP-A-60-249148 and 60-249149, and is a group represented by the following general formula. Here, the symbol * represents a position bonding to the left side in the general formula (I), and the symbol ** represents a position bonding to the right side in the general formula (I).

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, Is mentioned. Here, R ₆₉ has the same meaning as R ₄₁ described above, and R ₇₀ has the same meaning as R ₄₃ . R ₆₅ , R ₆₆
And R ₆₇ each represent a divalent group, and include the case where they are linked to form a cyclic structure. Specific examples of the group represented by formula (T-1) include the following groups.

＊ －SCH ₂ － ＊＊ (2) Group that causes a cleavage reaction by utilizing an 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, * indicates a position to be bonded on the left side in general formula (I), and ** indicates a position on the right side in general formula (I). 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 a group 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 a cleavage reaction of imino ketal.

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.

In formula (I), R is preferably an aromatic group,
₁₁ COOR units, -COR ₁₁ group, -OR ₁₁ group, -SR ₁₁ group, -SO ₂ R ₁₁ group, cyano group, halogen atom, heterocyclic group, Or represents a nitro group. Here, R ₁₁ and R ₁₂ have the same meanings as R ₄₁ and R ₄₃ described above, respectively. The meanings of the aromatic group, the heterocyclic group and the aliphatic group have the same meanings as described above.

In the general formula (I), X is The 5- or 6-membered nitrogen-containing heterocycle formed with is selected from the following.

In the formula, * mark represents a position to be bonded to A- (L) _a in the general formula (I), and ** mark represents the general formula (I). Represents the position to combine with.

R ₁₃ represents a substituent, and when the aromatic group has a substituent, those listed as examples of the substituent are preferable examples, and b is an integer of 0 to 2. When b is plural, plural R _13's represent the same or different. R ₁₄ represents an aliphatic group, an aromatic group or a heterocyclic group. R ₁₅ represents a hydrogen atom or a group having the same meaning as R ₁₃ . When b is 2 and two R _13's are present, each may be a divalent group to be bonded to each other to form a cyclic structure. A benzene condensed ring is mentioned as such an example.

Examples of the photographically useful group represented by PUG in the general formula (I) include a development inhibitor, a development accelerator, a nucleating agent, a coupler, a diffusible or non-diffusible dye, a desilvering accelerator, and a desilvering inhibitor. , Silver halide solvents, competing compounds, developing agents, auxiliary developing agents, fixing accelerators, fixing inhibitors, image stabilizers, color image stabilizers, photographic dyes, desensitizers, complexing with metal ions Ligands, fluorescent whitening agents, etc., or precursors thereof.

Typical of the above are development inhibitors. For example, tetrazolylthio group (for example, 1-phenyltetrazolylthio, 1- (4-methoxycarbonylphenyl) tetrazolitylthio, 1-ethyltetrazolylthio, 1-butyltetrazolylthio, 1- (2-methoxycarbonylethyl) tetrazolylthio. Or 1- (4-hydroxyphenyl) tetrazolylthio), 1,3,4-thiadiazolylthio group (for example, 5-methylthio-1,3,4-thiadiazolylthio, 5-butylthio-1,3,4- Thiadiazolytylthio, 5- (1-methoxycarbonylethylthio) -1,
3,4-thiadiazolylthio or 5- (2-methoxycarbonylethylthio) -1,3,4-thiadiazolylthio), 1,3,4-oxadiazolylthio group (for example, 5-methyl-1,3,4-oxadiazolylthio, 5-phenyl-
1,3,4-oxadiazolylthio), benzothiazolylthio group, benzoxazolylthio group, benzotriazolyl group (for example, 5-phenoxycarbonylbenzotriazolyl, 5,6-dimethylbenzotriazolyl, 5-bromobenzotriazolyl), a benzoindazolyl group and the like.

For examples and functions of development inhibitors and other PUGs, see US Pat. Nos. 4,248,962, 4,409,323, 4,47.
7,563, 4,390,618, 4,518,682, 4,555,477
Issue, Research Disclosure, 1973 Item No.1
1449 and JP-A-61-2201247.

When the group represented by PUG in formula (I) represents a bleaching accelerator, examples thereof include known bleaching accelerator residues. For example, various mercapto compounds such as those described in U.S. Pat.No. 3,893,858, British Patent No. 1,138,842 and JP-A-53-141623, JP-A-SHO
Compounds having a disulfide bond as described in JP-A-53-95630, thiazolidine derivatives as described in JP-B-53-9854, and isothiourea derivatives as described in JP-A-53-94927. , Shokoku Sho45−
8506, thiourea derivatives as described in JP-B-49-26586, thioamide compounds as described in JP-A-49-42349, described in JP-A-55-26506. And diarylenediamine compounds as described in U.S. Pat. No. 45-52834. These compounds are preferable examples in which a substitutable heteroatom contained in the molecule is bonded instead of PUG in the general formula (I).

When PUG represents a bleaching accelerator, it is more preferably a group represented by the following general formula (XII), (XIII) or (XIV).

In the formula, * indicates in general formula (I) R ₃₁ represents a position to be bonded to, R ₃₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, R ₃₂ represents a group having the same meaning as R ₃₁ , a divalent aliphatic group having 6 to 10 carbon atoms. It represents an aromatic group or a divalent heterocyclic group having a 3- to 8-membered ring, preferably a 5- or 6-membered ring, and X ₁ is -O-, -S-, -COO-, -SO.
_2- , X ₂ represents an aromatic group having 6 to 10 carbon atoms, X ₃ represents a 3- to 8-membered ring having at least one carbon atom bonded to S in the ring, preferably 5-membered or 6-membered. Represents a heterocyclic group of a member ring, Y ₁ is a carboxyl group or a salt thereof,
Sulfo group or salt thereof, hydroxyl group, phosphonic acid group or salt thereof, amino group (which may be substituted with an aliphatic group having 1 to 4 carbon atoms), -NHSO ₂ -R ₃₅ or -SO
₂ NH-R ₃₅ group (wherein salt means sodium salt, potassium salt, ammonium salt or the like), and Y ₂ is
Y ₁ represents a group or a hydrogen atom having the same meaning as described above, r represents 0 or 1, l represents an integer of 0 to 4, m represents an integer of 1 to 4, and u represents 0 to 4
Represents an integer. However, m Y ₁ are R ₃₁ − {(X ₁ ) _r −R ₃₂ } ₁ , X ₂ {(X ₁ ) _r −R ₃₂ } _l and X ₃ − {(X ₁ ) _r −R ₃₂ }. bound in substitutable positions of each of the l, m represents the m-number of Y ₁ when a plurality same or different, l is the l when a plurality {(X _{1) r}
-R ₃₂ } represents the same or different. Where R
₃₃ , R ₃₄ and R ₃₅ are each a hydrogen atom or a carbon number of 1 to 8,
Preferably, it represents 1 to 5 aliphatic groups. When R ₃₁ to R ₃₅ represent an aliphatic group, they may be linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted. It is preferably unsubstituted, but examples of the substituent include a halogen atom, an alkoxy group (eg, methoxy, ethoxy), an alkylthio group (eg, methylthio,
Ethylthio) and the like.

The aromatic group represented by X ₂ and the aromatic group when R ₃₂ represents an aromatic group may have a substituent. For example, those enumerated as the aliphatic substituents may be mentioned.

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

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

−SCH ₂ CH ₂ CO ₂ H −SCH ₂ CO ₂ H −SCH ₂ CH ₂ OH −SCH ₂ CH ₂ NH ₂ Specific examples of the group represented by -SCH ₂ CH ₂ NHCOCH ₃ formula (XIII) may include, for example the following.

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

The coupler of the present invention can be used in any layer such as a high sensitivity layer or a low sensitivity layer, and can also be used in a light sensitive silver halide emulsion layer or an adjacent layer thereof.

The addition amount of the compound represented by the general formula (I) of the present invention varies depending on the structure and use of the compound, but it is preferably 1 × 10 ⁻⁶ to 1 per mol of silver present in the same layer or adjacent layers.
Mol, particularly preferably 1 × 10 ⁻³ to 5 × 10 ⁻¹ mol.

The compound represented by formula (I) of the present invention may be used alone in a certain layer, or may be used in combination with a known coupler. When used in combination with another color image-forming coupler, the molar ratio of the compound of the present invention to the other color image-forming coupler (the coupler of the present invention / the other color image-forming coupler) is 0.1 / 99.9.
90 to 90/10, preferably 5/95 to 50/50.

The specific examples of the compounds represented by formula (I) of the present invention are shown below, but the invention is not limited thereto.

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

Compound 1 30g and 240g with chloroform 100ml
Mix with 30 ml of N, N-dimethylacetamide mixed solvent,
Warmed to 0 ° C. After reacting for 3 hours, cooled to room temperature,
200 ml of dichloromethane was added, 500 ml of 2% sodium hydroxide aqueous solution was added, and the mixture was vigorously stirred. The mixture was transferred to a separating funnel, the oil layer was collected, washed once with water, and then washed with diluted hydrochloric acid and water in this order. The oil layer was taken, the solvent was distilled off under reduced pressure, and the residue was separated and purified using column chromatography. Elution was performed using a mixed solvent of ethyl acetate and hexane at a ratio of 1: 3 to obtain 13.5 g of the desired exemplary compound (1).

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number of layers of the emulsion layer and the non-photosensitive layer and the layer order. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally such that the red-sensitive layer, green The color-sensitive layer and the blue color-sensitive layer are provided in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-113438.
No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler as described in the specification, DIR compounds and the like, and contains a color mixing inhibitor as commonly used. You can leave.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of high-speed emulsion layer and low-speed emulsion layer as described in No.
A layer structure can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751 and 62-62
No. 200350, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer on the side remote from the support,
A high sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the farthest side from the support, a low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL ) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / B
It can be installed in the order of L / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH / GL / RL
It can also be arranged in the order of. In addition, JP-A-56-25738
No. 62-63936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even in the case of being composed of three layers having different sensitivities as described above, Japanese Patent Laid-Open No.
As described in JP-A-202464, in the same color-sensitive layer, a medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side remote from the support.

As described above, various layer configurations and arrangements can be selected according to the purpose of each sensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may have a regular crystal such as a tetradecahedron, an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, 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 23, p. 22-23, "I. Emulsion production (Emulsion prepara
and types) ”, and No. 18716 (November 1979)
Mon), p. 648, "The Physics and Chemistry of Photography" by Graphide, published by Ballmontel (P.Glafkides, Chemie et Phisique P.
hotographique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photo
graphic Emulsion Chemistry (Focal Press, 1966)),
"Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al. Making and Coating
It can be prepared using the method described in Photographic Emulson, 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.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gaft, Gutoff Photographic Scinence 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, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded with a compound other than silver halide such as silver halide and lead oxide.

 Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding portions are summarized in the table below.

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

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,5
It is preferable to add to the light-sensitive material a compound capable of fixing by reacting with formaldehyde described in No. 03.

Various Lar couplers can be used in the present invention, and specific examples thereof are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760; U.S. Pat.No. 3,973,968;
No. 314,023, No. 4,511,649, European Patent No. 249,473A,
And the like are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent 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-60-3355.
2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-35.
No. 730, No. 55-118034, No. 60-185951, U.S. Patent No.
Those described in 4,500,630, 4,540,654, 4,556,630 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453.
A, U.S. Pat.Nos. 3,446,622, 4,333,999, and
Preferred are those described in 4,451,559, 4,427,767, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 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. 4,409,320, No. 4,576,910, British Patent No. 2,
No. 102,173, etc.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the above-mentioned RD17643, VII-F.
Patents described in paragraphs, JP-A-57-151944 and JP-A-57-1542
The compounds described in U.S. Pat. No. 34,60-184248 and U.S. Pat. No. 4,248,962 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include 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, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in U.S. Pat.
-185950, DIR redox compound releasing coupler or DIR coupler releasing coupler or DIR coupler releasing redox compound or DIR redox compound releasing redox described in JP-A-62-24252, etc. RD, a coupler that releases colored dyes
No. 11449 and No. 24241, bleach accelerator releasing couplers described in JP-A No. 61-201247 and the like, and ligand releasing couplers described in US Pat. No. 4,553,477 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 solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used for the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexyl phenylphosphonate, etc., benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-t-)
Amylphenol, etc.), fatty acid carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-) Butoxy-5-t-
Octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

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

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

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.No.
Development can be carried out by the usual methods described in 17643, pp. 28-29, and No. 18716, 651 left column to right column.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent. A p-phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acid, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal process is performed, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 or less per square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and the pH to high and using the color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used.
Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. . Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and persulfates are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution containing these aminopolycarboxylic acid iron (III) complex salts is usually
5.5 to 8, but lower p for faster processing
H can also be processed.

If necessary, a bleaching accelerator can be used before and after the bleaching solution, the bleach-fixing solution. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
No. 53-72623, No. 53-95630, No. 53-95631,
53-104232, 53-124424, 53-141623, and
53-28426, Research Disclosure No. 17129
Having a mercapto group or a disulfide group described in JP-A No. (July 1978); thiazolidine derivatives described in JP-A-50-140129;
20832, 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-5
Iodide salt described in 8-16235; West German Patent No. 966,410,
Polyoxyethylene compounds described in No. 2,748,430;
Polyamine compounds described in JP-B-45-8836; Other JP-A-49-42434, 49-59644, 53-94927, 54
-35727, 55-26506, 58-163940, compounds such as bromide ion can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are the compounds described in U.S. Pat. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when fixing a color light-sensitive material for photographing with a bleaching solution.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodide salts, and the use of thiosulfates is common.
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. 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), the application, and the temperature of rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Television Engineers Vol. 64, pp. 248-253 (5 May 1955)
It can be obtained by the method described in (Month issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1986 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry". It is also possible to use disinfectants described in "Techniques for sterilization, disinfection and fungicide of microorganisms" edited by the Society of Sanitary Engineers and "Encyclopedia of Fungicides and Fungicides" edited by the Japan Society of Antifungals and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9, and preferably 5-8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but are generally 20 seconds to 10 minutes at 15 to 45 ° C, and preferably 30
A range from seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.

Further, after the water washing treatment, a stabilization treatment may be further performed. As an example, a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photography, can be mentioned. . Various chelating agents and antifungal agents can be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

A color developing agent may be incorporated in the silver halide color light-sensitive material of the present invention for the purpose of simplifying and accelerating the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base-type compounds described in Research Disclosure 14850 and 15159, aldol compounds described in 13924, and metals described in U.S. Pat.No.3,719,492 Salt complex, JP 5
The urethane type compounds described in 3-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64339, JP-A-57-144547 and JP-A-58-115.
No. 438 is listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Further, the silver halide light-sensitive material of the present invention is described in US Pat.
500,626, JP-A-60-133449, 59-218443, 6
It can also be applied to the photothermographic materials described in 1-238056 and European Patent 210,660A2.

(Effect of the Invention) The silver halide photographic light-sensitive material of the present invention has excellent effects such as excellent sharpness, graininess, color reproducibility and desilvering property and high sensitivity.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 Sample 101, which is a multilayer color light-sensitive material, was prepared by layer-coating each layer having the composition shown below on a cellulose triacetate film support having an undercoat.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer: Antihalation layer Black colloidal silver 0.18 gelatin 0.40 Second layer: Intermediate layer 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U- 1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (6 mol% silver iodide, average grain size 0) .
6μ, variation coefficient for particle size 0.15) Silver 0.55 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 Sensitizing dye IV 4.0 × 10 ^-5 EX-2 0.350 HBS-1 0.005 EX-10 0.011 Gelatin 1.20 4th layer (2nd red-sensitive emulsion layer) Tabular silver iodobromide emulsion (10 mol% silver iodide, average grain size of 0.
7μ, average aspect ratio 5.5 average thickness 0.2μ) Silver 1.0 Sensitizing dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 Sensitizing dye IV 3.0 × 10 ^-5 EX -0.40 EX-3 0.050 EX-10 0.006 Gelatin 1.30 5th layer (3rd red emulsion layer) Silver iodobromide emulsion (16 mol% silver iodide, average grain size 1.1μ)
Silver 1.60 Sensitizing dye IX 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 Sensitizing dye IV 3.1 × 10 ^-5 EX-3 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 gelatin 1.63 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 EX-12 0.004 gelatin 0.80 7th layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 Mol%, average particle size 0.
6μ, average aspect ratio 6.0 average thickness 0.15) Silver 0.40 Sensitizing dye V 3.0 × 10 ^-5 Sensitizing dye VI 1.0 × 10 ^-4 Sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75 Eighth layer (second green emulsion layer) Monodisperse silver iodobromide emulsion (9 mol% silver iodide, average grain size of 0.
7μ, coefficient of variation 0.18) silver 0.80 sensitizing dye V 2.1 × 10 ^-5 sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.180 EX-8 0.010 EX-1 0.008 EX-7 0.012 HBS-1 0.160 HBS-4 0.008 Gelatin 1.10 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 12 mol%, average grain size 1.0μ)
Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-6 0.065 EX-11 0.030 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.74 10th layer (yellow filter layer) Yellow colloidal silver 0.05 EX-5 0.08 HBS-3 0.03 Gelatin 0.95 11th layer (1st blue sensitive emulsion layer) Tabular silver iodobromide emulsion (6 mol% silver iodide, Average particle size 0.
6μ, average aspect ratio 5.7 average thickness 0.15) Silver 0.24 Sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.85 EX-8 0.12 HBS-1 0.28 Gelatin 1.28 12th layer (2nd blue-sensitive emulsion layer) Monodisperse iodine odor Silver halide emulsion (silver iodide 10 mol%, average grain size 0.
8μ, coefficient of variation 0.16) silver 0.45 sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.20 EX-10 0.015 HBS-1 0.03 gelatin 0.46 layer 13 (third blue-sensitive emulsion layer) silver iodobromide emulsion (Silver iodide 14 mol%, average grain size 1.3μ)
Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (1st protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average particle size 0.07μ)
Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 1.00 Fifteenth layer (second protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) 0.54 S-1 0.15 S-2 0.05 Gelatin 0.72 In addition to the above components, a gelatin hardener H-1 and a surfactant were added.

(Samples 102 to 110) EX-10 of the third layer and the fourth layer of Sample 101 was replaced with the compounds listed in Table 2 at the molar ratios shown in Tables 102 to 110
Created 10.

These samples were subjected to white imagewise exposure and subjected to the following color development processing to determine the relative sensitivity of the density of fog +0.2 of a cyan image.

In addition, exposure for MTF measurement was applied, the same development processing was performed, and MTF values of magenta and cyan color images were calculated by a conventional method.

After uniform green light was applied, red light was subjected to increased exposure to perform the same development process. At this time, the magenta density of the red light unexposed area is about 1.40, the cyan density is about 0.2, and the value obtained by subtracting the magenta density at the exposure amount at which the cyan density becomes 2.0 from the density of the red light unexposed area as the interlayer effect. The results are shown in Table 1.

The color development was carried out at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each process is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hynoxylamine sulfate 2.4g 4- (N -Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5g Water added 1.0 pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0 pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0 pH6.6 Stabilizer Formalin (40%) 2.0ml Polyoxy Ethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g Water added 1.0 From Table 1, it is clear that the sample of the present invention has a large MTF value for magenta and cyan images, is excellent in sharpness, and is excellent in color reproduction represented by the interlayer effect.

HBS-1 tricresyl phosphate HBS-2 dibutyl phthalate HBS-3 bis (2-ethylexyl) phthalate Example 2 The sample produced in Example 1 was subjected to the same exposure as in Example 1 and processed by the processing method shown in Table 2 or Table 3 below. In all cases, the same results as those obtained in Example 1 were obtained.

 Table-2 Processing method Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 1 minute 00 seconds 38 ℃ Bleaching fixing 3 minutes 15 seconds 38 ℃ Washing (1) 40 seconds 35 ℃ Washing (2) 1 minute 00 seconds 35 ℃ stability 40 seconds 38 ℃ dry 1 minute 15 seconds 55 ℃ Next, write the composition of the treatment liquid.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5 Add water and add 1.0 pH 10.05 (Bleaching solution) (g) Ferric ammonium ethylenediaminetetraacetate dihydrate 120.
0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Ammonia water (27%) 15.0 ml Add water 1.0 pH 6.3 (Bleach fixer) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70 %) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 pH 7.2 (Washing liquid) Tap water is H type strong acid cation exchange resin (Amberlite IR-120B by Rohm and Haas) and OH type anion. Water was passed through a mixed bed column packed with exchange resin (Amberlite IR-400) to treat calcium and magnesium ions at a concentration of 3 mg / or less, followed by sodium diisocyanurate dichloride 20 mg / and sodium sulfate 150 mg /. Was added.

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

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to 1.0 pH 5.8 to 8.0 Table- 3 Processing method Step Processing time Processing temperature Color development 2 minutes 30 seconds 40 ° C Bleach fixing 3 minutes 00 seconds 40 ° C Water washing (1) 20 seconds 35 ° C Water washing (2) 20 seconds 35 ° C Stable 20 seconds 35 ° C Drying 50 seconds 65 ° C Next, the composition of the treatment liquid will be described.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N- (β-hydroxyethyl) amino) -2-methylaniline sulfate 4.5 Water was added to 1.0 pH 10.05 (bleach-fixing solution) (unit: g) Ethylenediaminetetraacetic acid Ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid Disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleach accelerator 0.01 mol 1.0 pH 6.0 by adding water (washing solution) Tap water was filled with H-type strongly acidic cation exchange resin Amberlite IR-120B manufactured by Rohm and Haas Co. and OH type anion exchange resin (Amberlite IR-400). Water was passed through a mixed-bed column to treat calcium and magnesium ions at a concentration of 3 mg / or less, and then sodium isocyanurate dichloride 20 mg / and sodium sulfate 1.5 g / were added.

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

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water is added to 1.0 pH 5.0 to 8.0

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula (I): (In the formula, A represents a group in which a bond with a residue other than A is cleaved by reacting with an oxidized product of a developing agent, and L is a bond with a residue except L after the bond with A is cleaved. Represents a group which is cleaved, and X is Together with represents an organic residue for forming a 5-membered heterocyclic ring selected from the following, R represents a hydrogen atom, a substituent or PUG, PUG represents a photographically useful group, and a represents 0
Or represents 1. ) In the formula, * indicates the position of bonding with A- (L) _a- in the general formula (I), and ** indicates in the general formula (I). Represents the position to combine with. R ₁₃ represents a substituent, and b is an integer of 0 to 2.
When b is plural, plural R _13's represent the same or different. R ₁₄ represents an aliphatic group, an aromatic group or a heterocyclic group. R ₁₅ represents a hydrogen atom or a group having the same meaning as R ₁₃ . When b is 2 and two R _13's are present, each may be a divalent group to be bonded to each other to form a cyclic structure.