JP2668810B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material containing a compound which makes a development inhibitor available during development processing.

[0002]

2. Description of the Related Art In a subtractive color photographic light-sensitive material,
Conventionally, development inhibitor releasing couplers (DIR couplers) have been used for the purpose of improving photographic performance such as sharpness, granularity or color reproducibility. For the photographic effects of DIR couplers, see TH James, "The Theory of Photographic."
Process ", 4th ed., Pp610-611 and pp344 (1977, MACMIL
LAN PUBLISHING Co., New York).

As a DIR coupler used in the green-sensitive emulsion layer, one that releases a development inhibitor at the time of development by a coupling reaction with an oxidized developing agent and forms a magenta dye at the same time as the color reproduction of a light-sensitive material is considered. It is preferable from the viewpoint of sharpness. This is because the use of a DIR coupler that forms a magenta dye in the green-sensitive emulsion layer makes it possible to use the dye formed from the DIR coupler as a part of the magenta density, and therefore, compared to the case where a DIR coupler that does not form a magenta dye is used. This is because the total amount of organic compounds such as couplers added to the green-sensitive emulsion layer can be reduced, and the effect of improving sharpness by thinning can be obtained.

As a DIR coupler which forms magenta, a coupler having a 5-pyrazolone nucleus is well known.
The DIR coupler of the 5-pyrazolone mother nucleus had the drawback of low thermal stability. A DIR coupler is a compound which has a property of strongly acting on a silver halide and greatly changing the performance of a light-sensitive material, and is provided directly or via a linking group at a coupling active position of the coupler so as to protect its active site. By bonding, they are designed to be in an inert state until development occurs. However, if the thermal stability of the DIR coupler is low, the D
The IR coupler is decomposed to produce a substance which adversely affects the photographic performance, resulting in fatal deterioration of the photographic performance. This danger increases as the amount of DIR coupler used increases. Therefore, when a DIR coupler having a low thermal stability of 5-pyrazolone nucleus is used, the amount of addition must be increased too much. There is a restriction that you can not.

On the other hand, DI of a pyrazoloazole skeleton, which has been actively researched as a new magenta coloring skeleton in recent years,
Although R couplers are described in JP-A-61-28947, such DIR couplers have improved thermal stability, but do not have sufficient performance in terms of the layering effect and sharpness. Did not. Also, JP-A-3-142
The DIR coupler described in Japanese Patent No. 447 has both an improved thermal stability and an improved overlay effect and sharpness to some extent. However, an improvement in the overlay effect and sharpness has been desired. . Further, the photosensitive material to which the coupler described in the specification is added tends to cause a decrease in sensitivity when the photosensitive material before development is stored under high temperature and humidity conditions, despite the high thermal stability of the coupler. Therefore, improvement of this point was necessary. Further, it has become clear that the light fastness of the magenta dye produced by the development processing is not always satisfactory.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to develop a magenta-colored DIR coupler which has a large effect of improving the layering effect and sharpness and which solves the problems relating to the storage stability and light fastness of a photosensitive material. The object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent storage stability, excellent sharpness, granularity and color reproducibility.

[0007]

An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a development inhibitor releasing coupler represented by the following general formula (I). Achieved.

[0008]

Embedded image (In the formula, R ₁ and R ₂ represent an aliphatic group or an aromatic group, and R ₃ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a hydroxyl group,
An alkoxy group, an aryloxy group, a heterocyclic oxy group,
Acyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carbamoyloxy, sulfamoyloxy, sulfonyloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, amino, anilino, hetero Ring amino group, amide group, alkoxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, azo group, nitro group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group, sulfonyl group, sulfamoyl group , Sulfo group and phosphinyl group, and n represents an integer of 0 to 3. Z ₁ and Z ₂ each independently represent = N- or = C (R ₄ )-, and R
₄ has the same meaning as R ₃ . Both Z ₁ and Z ₂ =
When it is C (R ₄ )-, two R _{4 s} may be the same or different. R _{1 to} R ₄ may form a bis form with a divalent group. DI represents a development inhibitor residue. )

The inventors of the present invention have made extensive studies by paying attention to the substituent of the carbon atom adjacent to the coupling active position of the pyrazoloazole magenta coupler, and as a result, have studied the electronic effect and steric effect of the substituent. By adjustment, a DIR coupler having a magenta color which achieves the object of the present invention has been reached.

The compound represented by formula (I) of the present invention will be described in detail below. The aliphatic group represented by R ₁ and R ₂ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 32 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, 1-butyl, t -Butyl, 1-hexyl, 1-octyl, 1-
Represents decyl, cyclopropyl, cyclohexyl, vinyl, acetylenyl. The aromatic group represented by R ₁ and R ₂ is an aromatic group having 6 to 32 carbon atoms, and represents, for example, phenyl, 1-naphthyl, or 2-naphthyl. R ₁ and R
_The aliphatic group and the aromatic group represented by ₂ may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

R ₃ is a halogen atom (for example, a fluorine atom or a chlorine atom), an aliphatic group (a linear, branched or cyclic alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group or an alkynyl group, for example, , Methyl, ethyl,
Isopropyl, 1-butyl, t-butyl, 1-octyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), an aryl group (an aryl group having 6 to 32 carbon atoms,
For example, phenyl, p-tolyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-nitrophenyl, 4-ethoxyphenyl, 1-naphthyl), heterocyclic group (having 1 to 32 carbon atoms). And a saturated or unsaturated heterocyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl 1-piperidinyl), cyano group, carboxyl group, hydroxyl group, alkoxy group (carbon Alkoxy groups having 1 to 32, for example, methoxy, ethoxy, 1-butoxy), aryloxy groups (aryloxy groups having 6 to 32 carbon atoms, such as phenoxy, 2-methoxyphenoxy, 4-nitrophenoxy, 3 -Butanesulfonamidophenoxy,
2,5-di-t-amylphenoxy, 2-naphthoxy), heterocyclic oxy group (a heterocyclic oxy group having 1 to 32 carbon atoms, such as 2-furyloxy, 1-phenyltetrazole-5-oxy, 2 -Tetrahydropyranyloxy), an acyloxy group (an acyloxy group having 1 to 32 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy, etc.), an alkoxycarbonyloxy group (an alkoxycarbonyloxy group having 1 to 32 carbon atoms) In, for example, ethoxycarbonyloxy,
t-butoxycarbonyloxy, 2-ethyl-1-hexyloxycarbonyloxy), aryloxycarbonyloxy group (C6-C32 aryloxycarbonyloxy group, for example, phenoxycarbonyloxy), carbamoyloxy group (carbon number 1 to 32 carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), sulfamoyloxy groups (sulfamoyloxy groups having 32 or less carbon atoms, such as N, N- Diethylsulfamoyloxy, N-propylsulfamoyloxy), a sulfonyloxy group (a sulfonyloxy group having 1 to 32 carbon atoms,
For example, methanesulfonyloxy, benzenesulfonyloxy), an acyl group (an acyl group having 1 to 32 carbon atoms, for example, acetyl, pivaloyl, benzoyl), an alkoxycarbonyl group (an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, Ethoxycarbonyl, isobutyloxycarbonyl), an aryloxycarbonyl group (an aryloxycarbonyl group having a carbon number of 7 to 32, such as phenoxycarbonyl), a carbamoyl group (a carbon number of 1 to 3).
2 carbamoyl groups, for example, N, N-dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N
-Propylcarbamoyl), an amino group (an amino group having 32 or less carbon atoms, for example, amino, N-methylamino,
N, N-dioctylamino), anilino group (having 6 to 6 carbon atoms)
32 anilino groups, such as N-methylanilino, 2
-Chloro-5-tetradecanamidoanilino, 2-chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecanamido} anilino), heterocyclic amino (heterocyclic amino having 1 to 32 carbon atoms) Group, for example, 4-
Pyridylamino), an amide group (an amide group having 1 to 32 carbon atoms, for example, acetamido, benzamide, tetradecaneamide, 2- (2,4-di-t-amylphenoxy) butanamide, 2- {4- (4-hydroxy Phenylsulfonyl) phenoxydodocanamide), alkoxycarbonylamino group (alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, t-butoxycarbonylamino, ethoxycarbonylamino), ureido group (ureido group having 1 to 32 carbon atoms) For example, N, N-dimethylureide, N-phenylureide), a sulfonamide group (a sulfonamide group having 1 to 32 carbon atoms, such as methanesulfonamide, butanesulfonamide, p
-Toluenesulfonamide, 2-octyloxy-5-
t-octylbenzenesulfonamide), a sulfamoylamino group (a sulfamoylamino group having a carbon number of 32 or less, for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino) ,
Azo groups (azo groups having 32 or less carbon atoms, such as phenylazo and 4-methoxyphenylazo), nitro groups, and alkylthio groups (alkylthio groups having 1 to 32 carbon atoms such as ethylthio, octylthio, tetradecylthio,
-Phenoxypropylthio), an arylthio group (an arylthio group having 6 to 32 carbon atoms, for example, phenylthio,
4-dodecylphenylthio, 2-butoxy-4-t-octylphenylthio, 4-tetradecanamidophenylthio), a heterocyclic thio group (a heterocyclic thio group having 1 to 32 carbon atoms, for example, 1-phenyltetrazoli Ru-5-thio), a sulfinyl group (a sulfinyl group having 1 to 32 carbon atoms, for example, benzenesulfinyl, 3,5-di-
(Dodecyloxycarbonyl) benzenesulfinyl), a sulfonyl group (a sulfonyl group having 1 to 32 carbon atoms, for example, methanesulfonyl, octanesulfonyl,
p-toluenesulfonyl), a sulfamoyl group (sulfamoyl group having 32 or less carbon atoms, for example, N, N-dimethylsulfamoyl, N, N-dibutylsulfamoyl), a sulfo group, and a phosphinyl group. Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Next, preferred ranges of these substituents will be described. R ₁ and R ₂ are preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferred alkyl groups are methyl, ethyl, propyl, and 1-butyl.

R ₃ is preferably a hydrogen atom, having 1 to 1 carbon atoms.
It is an alkyl group or a phenyl group of 0, and n is preferably 0 or 1.

R ₄ and R ₃ have the same meanings, but preferably R ₄ represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group represented by R ₄ has the same meaning as the aliphatic group represented by R ₁ and R ₂ described above. The aromatic group represented by R ₄ has the same meaning as the aromatic groups represented by R ₁ and R ₂ described above. The heterocyclic group represented by R ₄ is a saturated or unsaturated heterocyclic group having 1 to 32 carbon atoms, for example, 2-thienyl, 4-pyridyl,
It represents a 2-furyl, 2-pyrimidinyl or 1-pyridyl 1-piperidinyl group. The aliphatic group, aromatic group or heterocyclic group represented by R ₄ may further have a substituent, and preferable substituents are the same as those exemplified as the group represented by R ₃ .

R ₄ is more preferably an alkyl group or an aromatic group, and an aromatic group is particularly preferable in that the effect of improving the overlay effect and the sharpness is greater. Preferred alkyl groups as R ₄ are those represented by the following general formula (L-1).

General formula (L-1) -C (R ₄₁ ) (R ₄₂ ) -R ₄₃

In the formula, R ₄₃ has the same meaning as R ₃ described above, and R ₄₁ and R ₄₂ each represent an alkyl group having 1 to 32 carbon atoms. Preferred alkyl groups represented by R _{41 and} R ₄₂ are alkyl groups having 32 or less carbon atoms (eg, methyl, ethyl, propyl, hexyl, nonyl, undecyl, tridecyl, hexadecyl), and further having a substituent. May be. R ₄₃ has the same meaning as the substituent represented by R ₃ , and is preferably a hydrogen atom or an alkyl group. Preferred examples of the alkyl group include those described as preferred examples of the alkyl group represented by R _41. It is the same and may further have a substituent. R ₄₁ , R ₄₂
And when the group represented by R ₄₃ further has a substituent, preferred substituents are the same as those listed as the group represented by R ₃ .

A preferred aromatic group for R ₄ is a phenyl group, which may further have a substituent. When it further has a substituent, preferable substituents are the same as those mentioned as the group represented by R ₃ .

Examples of the development inhibitor represented by DI in the general formula (I) include US Pat. No. 4,477,56.
3, JP-A-60-218644, and JP-A-60-2117.
No. 50, No. 60-233650 or No. 61-1174
No. 3 is mentioned.

Preferred development inhibitors represented by DI in the general formula (I) are those represented by the following general formula (II).

* -Y _1- (Y ₂ -LY ₃ ) _a (II)

(In the formula, the * mark represents the position of bonding to the pyrazolotriazole nucleus in the general formula (I). Y ₁ represents the basic skeleton of the development inhibitor, and Y ₂ represents ₂ having 8 or less carbon atoms.
L represents a valent linking group or a mere bond, and L represents a compound represented by the general formula (II)
A linking group containing a bond that is cleaved by a developer,
₃ represents a group for exhibiting a development inhibiting action. a is 0
Represents an integer of 1 to 3. )

Examples of the group represented by Y ₁ include a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, an imidazolylthio group, a benzimidazolylthio group, a benzothiazolylthio group and a benzoxazolylthio group. Typical examples are a tetrazolylseleno group, a benzotriazolyl group, a triazolyl group substituted with an alkylthio group, and a benzimidazolyl group.

The above-mentioned development inhibitor, after being cleaved from the pyrazolotriazole nucleus of the formula (I), diffuses in the photographic layer while exhibiting a development-inhibiting action, and partially flows out into the developer.
When a is not 0 in the general formula (II), the development inhibitor that has flowed out into the developer reacts with hydroxyl ions or hydroxylamine generally contained in the processing solution to contain the chemical contained in L. The bond portion is rapidly decomposed (for example, ester bond is hydrolyzed), the group represented by Y ₃ is cleaved, and the compound becomes a highly water-soluble compound having a small development inhibitory property, so that the development inhibitory effect is substantially disappeared.

The divalent group represented by Y ₂ is preferably -O-, -S-, -NHCO-, -SO ₂ -,-
CO- or -NHSO ₂ - represents a divalent linking group or a single bond of those aliphatic include group or aromatic containing heteroatoms such as represented by. When Y ₂ represents a divalent linking group, Y ₂ and to such as methylene, ethylene, _{propylene, -CH (CH 3) -,} - SCH 2 -,
_{-SCH (CH 3) -, -} CH 2 OCH 2 -, - SCH
Examples include a ₂ CH ₂ — or —CH ₂ SCH ₂ — group.

The linking group represented by L contains a chemical bond that is cleaved in a developer. Such chemical bonds include the following. Each of these is cleaved by a nucleophilic reactant such as hydroxyl ion or hydroxylamine which is a component in the color developing solution.

The cleavage reaction of chemical bonds left bond contained in the L (OH ^- reaction _{with) -COO- -COOH + HO- -NHCOO- -NH 2} + HO- -SO 2 O- -SO 3 H + HO _{- -CH 2 CH 2 SO 2 -} -OH + CH 2 = CHSO 2 - -OCO 2 - -OH + HO- -NHCOCO 2 - -NH 2 + HO-

In the case of a heterocyclic ring or a benzene condensed ring constituting the development inhibitor, the linking group represented by L is linked to the benzene ring portion via Y ₂ and directly linked to Y ₃ .

Y ₃ is a saturated or unsaturated, linear, branched or cyclic aliphatic group having 1 to 12 carbon atoms (eg, methyl, ethyl, propyl, hexyl, trifluoromethyl (eg, 3-methyl-1 -Butoxy) carbonylmethyl, 1-butoxycarbonylmethyl, 1-pentylaminocarbonylmethyl, allyl, propargyl, cyclohexyl), an aromatic group having 6 to 18 carbon atoms (eg, phenyl, naphthyl) or a heteroatom having 1 to 12 carbon atoms Cyclic group (for example, 2-pyridyl, 4-pyridyl, 2-furyl, 2-
Tetrahydrofuryl, 4-pyrazolyl), and more preferably Y ₃ is an aliphatic group having 1 to 10 carbon atoms or a phenyl group. The group represented by Y ₃ may further have a substituent, and preferred substituents are the same as those described as the group represented by R ₃ , and more preferably a halogen atom, having 1 to 10 carbon atoms. Alkoxy group, carbon number 6
-10 aryloxy group, C1-10 heterocyclic oxy group, C1-10 acyloxy group, C2
10 to 10 alkoxycarbonyloxy groups, 7 to 1 carbon atoms
0 aryloxycarbonyloxy group, having 1 to 1 carbon atoms
A carbamoyloxy group having 0, a sulfamoyloxy group having 1 to 10 carbon atoms, a sulfonyloxy group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, and having 7 carbon atoms An aryloxycarbonyl group having 10 to 10, a carbamoyl group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an anilino group having 6 to 10 carbon atoms,
Heterocyclic amino group having 1 to 10 carbon atoms, amide group having 1 to 10 carbon atoms, alkoxycarbonylamino group having 2 to 10 carbon atoms, ureido group having 1 to 10 carbon atoms, sulfonamide group having 1 to 10 carbon atoms, A sulfamoylamino group having 1 to 10 carbon atoms, a nitro group, an alkylthio group having 1 to 10 carbon atoms,
They are an arylthio group having 6 to 10 carbon atoms, a heterocyclic thio group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, a sulfonyl group having 1 to 10 carbon atoms, and a sulfamoyl group having 1 to 10 carbon atoms.

Particularly preferred as the development inhibitor represented by DI in the general formula (I) is the following general formula (DI-
1) and (DI-2).

[0031]

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[0032]

Embedded image (In the formula, an asterisk (*) represents a position bonded to the pyrazoloazole nucleus in the general formula (I). Z ₃ is a carbon atom and a nitrogen atom which are necessary for forming a heterocycle (single ring or condensed ring). It represents a metal atom group, Z ₄ is .Y ₂ and Y ₃ represents a non-metallic atomic group necessary for forming a heterocyclic ring (monocyclic or condensed) together with the nitrogen atom of Y ₂ and in formula (II) Y ₃ to be the same meaning.)

Z ₃ is preferably 5 together with -C = N-.
Represents a nonmetallic atomic group necessary for forming a heterocyclic ring which may be a substituted or condensed ring having 7 to 7 members. Examples of such heterocycles include triazole, tetrazole, oxadiazole, thiadiazole, benzimidazole or benzothiazole. Particularly preferred among these are 1,2,4-triazole, tetrazole, 1,3,4-oxadiazole,
1,3,4-thiadiazole.

Z ₄ is preferably 5 to 5 together with the nitrogen atom.
Represents a nonmetallic atomic group necessary for forming a 7-membered heterocyclic ring which may be substituted or fused. Examples of such heterocycles are imidazole, 1,2,2
4-triazole, 1,2,3-triazole, benzotriazole, pyrazole, indazole, imidazolidine-2-thione, oxazolidin-2-thione, 1,
2,4-triazoline-3-thione or 1,3,4-thiadiazoline-2-thione may be mentioned. Particularly preferred among these are 1,2,3-triazole and benzotriazole.

When the heterocyclic ring represented by formulas (DI-1) and (DI-2) has a substituent at a substitutable position other than -Y ₂ -LY ₃ , a preferable substituent is R ₃ . It is the same as those mentioned as the group represented, more preferably a halogen atom, an alkoxy group having 1 to 10 carbon atoms,
An aryl group having 6 to 10 carbon atoms, a heterocyclic group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms,
0 alkoxycarbonyloxy group, C 7-10 aryloxycarbonyloxy group, C 1-10 carbamoyloxy group, C 1-10 sulfamoyloxy group, C 1-10 sulfonyl An oxy group,
An acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms,
-10 amide group, C 2-10 alkoxycarbonylamino group, C 1-10 ureido group, C 1
A sulfonamide group of 10 to 10, a sulfanoylamino group of 1 to 10 carbon atoms, a nitro group, an alkylthio group of 1 to 10 carbon atoms, an arylthio group of 6 to 10 carbon atoms,
A 10-membered thio ring, a sulfinyl group having 1 to 10 carbon atoms, a sulfonyl group having 1 to 10 carbon atoms, and a sulfamoyl group having 1 to 10 carbon atoms.

The most preferable development inhibitor represented by DI in the general formula (I) is the following general formula (DI-
3) and (DI-4).

[0037]

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[0038]

Embedded image (In the formula, * represents the position to be bonded to the pyrazolotriazole nucleus in the general formula (I). Z ₃ , Z ₄ , Y ₂ and Y ₃ are the same as those in the general formulas (DI-1) and (DI-2). Z
₃ have the same meanings as Z _4, Y ₂ and Y _3. )

Hereinafter, specific examples of the development inhibitor represented by the general formula (II) of the present invention will be shown, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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The coupler represented by the general formula (I) includes
The couplers represented by the following general formulas (III), (IV), (V) and (VI) are included.
Couplers represented by formulas (III) and (IV) are particularly preferred in view of thermal stability, and couplers represented by formula (III) are particularly preferred in view of high coupling reactivity with an oxidized developing agent.

[0045]

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[0046]

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[0047]

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[0048]

Embedded image (Wherein, _{R 1, R 2, R 3} , R ₄ and DI are _{R 1, R 2, R 3} , the same meaning as R ₄ and DI in formula (I). In general formula (V) In the formula, two R ₄ may combine to form an aromatic ring.)

The compound represented by the general formula (I) may form a dimer or more multimer through a divalent or more valent group in the substituent R ₁ , R ₂ , R ₃ or R ₄ . When the compound represented by the general formula (I) forms a polymer, a homopolymer or a copolymer of an addition-polymerizable ethylenically unsaturated compound (color-forming monomer) having the above-mentioned compound residue is typical. In this case the multimer contains repeating units of the general formula (VII). The polymer may contain one or more kinds of color-forming repeating units, or may be a copolymer containing one or more non-color-forming ethylene-like monomers as a copolymer.

[0050]

Embedded image (Wherein, R ₃₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, E represents —CONH—, —CO ₂ —, or a substituted or unsubstituted phenylene group, and G represents a substituted or unsubstituted phenylene group. Represents a substituted alkylene group, phenylene group or aralkylene group, and T represents -CONH-, -NHC
_{ONH -, - NHCO 2 -,} - NHCO -, - OCON
H -, - NH -, - CO 2 -, - OCO -, - CO-,
_{-O -, - SO 2 -,} - NHSO 2 - or -SO ₂ NH
Represents-. f, g and t represent 0 or 1;
Neither g nor t is 0. QQ represents a compound residue obtained by removing a hydrogen atom from the compound represented by the general formula (I).

As the multimer, a copolymer of a compound monomer giving the compound unit of the general formula (VII) and the following non-color-forming ethylene-like monomer is preferable.

The non-color-forming ethylene-like monomers which do not couple with the oxidized form of the aromatic primary amine developing agent include:
Acrylic acid, α-chloroacrylic acid, α-alkacrylic acid (eg, methacrylic acid) Esters or amides derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide) , Diacetone acrylamide, methylene bis acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate,
n-butyl acrylate, t-butyl acrylate, i
so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate,
n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, eg, vinyl toluene) , Divinylbenzene, vinylacetophenone and sulfostyrene) itaconic acid, citracone, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg, vinyl ethyl ether) maleate, N
-Vinyl-2-pyrrolidone, N-vinylpyridine and the like.

Particularly preferred are acrylic acid ester, methacrylic acid ester and maleic acid ester. Two or more non-color-forming ethylene-like monomers used herein can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the art of polymer couplers,
When synthesizing a polymer coupler containing a repeating unit represented by the general formula (VII), the non-color-forming ethylene-like monomer copolymerized with the ethylene-like monomer having a coupler residue of the present invention is used as a copolymer. The physical and / or chemical properties of the polymer, such as solubility, the compatibility of the photographic colloid composition with a binder such as gelatin, its plasticity, thermal stability, etc., can be selected to be favorably affected. .

The polymer compound used in the present invention (lipophilic polymer compound obtained by polymerization of a vinyl monomer to give the compound unit represented by the general formula (VII)) dissolved in an organic solvent is used as an aqueous gelatin solution. It may be prepared by emulsion-dispersing it in the form of latex, or may be prepared by direct emulsion polymerization.

A method for emulsifying and dispersing a lipophilic polymer compound in an aqueous gelatin solution in the form of a latex is described in US Pat. No. 3,451,820, and emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,080. The method described in 370,952 can be used.

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

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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The method for synthesizing the compound represented by formula (I) of the present invention will be described below. 1H-pyrazolo [1,5-b] -1,2,4 contained in the compound represented by the general formula (III) among the compounds represented by the general formula (I)
-The triazole skeleton is disclosed in U.S. Pat. No. 4,540,654.
No., JP-B-2-44051, JP-A-60-17298
No. 2, No. 60-215687, No. 60-197688
Nos., 60-190779, 62-209457
No. 63-41851, No. 63-307453, and the like.

Of the compounds represented by the general formula (I),
The 1H-pyrazolo [5,1-c] -1,2,4-triazole skeleton contained in the compound represented by the general formula (IV) is described in U.S. Pat. No. 3,725,067, and JP-B-47-2744.
4, JP-A-48-30895, JP-A-61-18780.
And JP-A-62-33177, JP-A-1-233285, and the like.

Of the compounds represented by the general formula (I),
The 1H-imidazo [1,2-b] pyrazole skeleton contained in the compound represented by the general formula (V) is disclosed in JP-A-59-16.
2548, EP 119741 and WO8.
It can be synthesized by the method described in 6/02467.

Among the compounds represented by the general formula (I),
The 1H-pyrazolo [1,5-d] tetrazole skeleton contained in the compound represented by the general formula (VI) is disclosed in
It can be synthesized by the method described in 3552.

The introduction of a coupling-off group is described in JP-A-2-5.
It can be carried out as follows by the method described in the specification of No. 9584. That is, it is a method in which the coupling active site of pyrazoloazole is brominated with a reaction agent such as N-bromosuccinimide or bromine, and then a development inhibitor group is introduced.

[0074]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , Z ₁ , Z ₂ and DI represent R ₁ , R ₂ , R ₃ , Z ₁ , Z ₂ and D in the general formula (I))
Represents the same meaning as I. )

As the base used in the above reaction (2), an inorganic base such as sodium hydride or lithium aluminum hydride, potassium t-butoxide, sodium ethoxide, sodium methoxide, triethylamine,
N, N, N, N-tetramethylguanidine, 2,6-lutidine, 1,8-diazabicyclo [5,4,0] -7-
Organic bases such as undecene (DBU) are preferred. The solvent used in the reaction (2) is preferably an aprotic polar solvent, for example, 1,3-dimethylimidazolidine-2.
-One, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethyl Acetamide (DM
AC) and acetonitrile.

DI is represented by the general formula (DI-1) or (DI-
In the case of the group represented by 3), it can also be synthesized by the reaction represented by the following formula.

[0077]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , Z ₁ , Z ₂ and DI represent R ₁ , R ₂ , R ₃ , Z ₁ , Z ₂ and D in the general formula (I))
Represents the same meaning as I. Y represents a halogen atom (eg, chlorine atom, bromine atom), an imide group (eg, succinimide group, phthalimide group), a sulfonyl group (eg, benzenesulfonyl group), or the like. )

The preferred solvent used in this reaction is
Aprotic polar solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), acetonitrile, tetrahydrofuran, 1,4-
Examples thereof include ether solvents such as dioxane and 1,2-dimethoxyethane, halogen solvents such as dichloromethane, chloroform and 1,2-dichloroethane, and ethyl acetate.

Specific examples of the synthesis of the compounds of the present invention are shown below, but the present invention is not limited by these.

Synthesis Example 1 (Synthesis of Exemplified Compound (2)) Synthesis was carried out by the reaction shown in Chemical formula 29 below.

[0081]

Embedded image

11.7 g (11.5 mmol) of the intermediate (A) was dissolved in 100 ml of chloroform and cooled in a water bath with stirring. 2.05 g (11.5 mmol) of N-bromosuccinimide was added thereto and stirred for 10 minutes. The reaction mixture was washed twice with 100 ml of water, then dried over anhydrous sodium sulfate and concentrated. Intermediate (B) 1 was crystallized from a mixed solvent of ethyl acetate / hexane.
0.4 g was obtained. 1,3-dimethylimidazolidine-2
1.14 g (28.5%) of sodium hydride (dispersed in mineral oil, content 60% by weight) in 50 ml of -ON (DMI)
mmol) and cooled in an ice-water bath with stirring. To this, 8.31 g (28.5 mmol) of the intermediate (C) was added little by little over 10 minutes. After removing the ice water bath and stirring for further 10 minutes, the previously synthesized intermediate (B) was added and
Stirred at 0 ° C. for 2 hours. After cooling, 150 ml of ethyl acetate and 150 ml of water were added to the reaction mixture for extraction. The organic layer was washed twice with 150 ml of saturated aqueous sodium hydrogen carbonate, once with 150 ml of dilute hydrochloric acid, and further with 150 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography (eluent: hexane / ethyl acetate mixed solvent) to give 5.0 g (yield 40%) of Exemplified compound (2). Obtained as a pale yellow-orange glassy solid. Mass spectrum (FAB, Negative) m / e = 1302 ([M−H] ⁻ ).

Synthesis Example 2 (Synthesis of Exemplified Compound (5)) Synthesis was carried out by the reaction shown in the following Chemical Formula 30.

[0084]

Embedded image

23.0 g (31.8 mmol) of the intermediate (D) were dissolved in 200 ml of chloroform and cooled in a water bath with stirring. N-bromosuccinimide 5.
53 g (31.1 mmol) was added and stirred for 25 minutes. The reaction mixture was washed twice with 150 ml of water, dried over anhydrous magnesium sulfate and concentrated to obtain an intermediate (E). 1,3-Dimethylimidazolidin-2-one (DM
I) 3.82 g (95.4 mmol) of sodium hydride (dispersed in mineral oil, content 60% by weight) was added to 90 ml, and the mixture was cooled in an ice-water bath with stirring. Intermediate (C)
27.8 g (95.4 mmol) were added portionwise over 20 minutes. After removing the ice-water bath and stirring for another 10 minutes, the intermediate (E) synthesized above was added, and the mixture was added at 95% to 1.
Stir for 5 hours. After cooling, the reaction mixture was treated with ethyl acetate 40
Extraction was performed by adding 0 ml and 500 ml of water. The organic layer was washed twice with 300 ml of saturated aqueous sodium bicarbonate, once with 300 ml of dilute hydrochloric acid and further with 300 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography (eluent; mixed solvent of hexane / ethyl acetate) to give Exemplified Compound (5) 18.4 (yield 57).
%) As a pale orange glassy solid. Mass spectrum (FAB, Negative) m / e = 1011 ([M−H] ⁻ ).

The development inhibitor-releasing coupler of the present invention may be used in any layer in a light-sensitive material, but is preferably added to a light-sensitive silver halide emulsion layer and / or a layer adjacent thereto. It is more preferably added to the emulsion layer, particularly preferably to the green-sensitive silver halide emulsion layer. The amount of these compounds added to the light-sensitive material is 3 × 10 ^-7 to 1 × 10 ^-3 mol / m ² , preferably 3 × 10 ^{-6 to} 7 × 10 ^-4 mol / m ² , and more preferably Is 1 × 1
It is 0 ⁻⁵ to 4 × 10 ⁻⁴ mol / m ² .

In the present invention, similarly to ordinary silver halide color photographic light-sensitive materials, preferably a yellow dye-forming coupler (hereinafter referred to as a yellow coupler), a magenta dye-forming coupler (hereinafter referred to as a magenta coupler), and a cyan dye A forming coupler (hereinafter, referred to as a cyan coupler) is used. The amounts of these yellow, magenta and cyan couplers used are not particularly different from those of ordinary silver halide color photographic materials.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein 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. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

In the intermediate layer, there is disclosed in JP-A-61-43748.
No. 59-113438, No. 59-113440
Couplers, DIR compounds and the like described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

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 a middle layer. In addition, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is arranged, and an arrangement of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. In addition, the arrangement may be changed as described above even in the case of four or more layers.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, and 4,707,436, and JP-A-62-160448.
And BL and G described in JP-A-63-89580.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL is disposed adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is about 2 mol%
Silver iodobromide or silver iodochlorobromide containing from about 1 to about 25 mol% of silver iodide.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2 μm
The following fine particles or large-sized particles having a projected area diameter of about 10 μm may be used, and a polydisperse emulsion or a monodisperse emulsion may be used.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23, "
I. Emulsion preparation and types ",
No. 18716 (November 1979), 648
No. 307105 (November 1989), 863
865 pages, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et Phisique Ph.
otographique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Chemistry (Focal Press, 196
6)), "Manufacture and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making an
d Coating Photographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4).

US Pat. Nos. 3,574,628, and 3,
Monodisperse emulsions described in, for example, 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 in Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,43
It can be easily prepared by the methods described in 3,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, the inside and the outside may have different halogen compositions, or may have a layered structure. Also, silver halides having different compositions are joined by epitaxial joining. May be
Further, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion may be of a surface latent image type formed on the surface by using a latent image as a seed, an internal latent image type formed inside the grains, or a type having a latent image on both the surface and the inside. It must be a negative emulsion. Of the internal latent image type, the core / core described in JP-A-63-264740 is used.
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
No. 3542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion usually used is one subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are described in Research Disclosure Nos. 17643, 18716 and N
o. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two types of emulsions having at least one characteristic different from one another in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The silver halide grains having a fogged surface described in US Pat. No. 4,082,553, and the inside of the grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are covered. Silver halide grains and colloidal silver can be preferably used in a photosensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. A silver halide grain having a grain inside or a surface fogged is
This refers to silver halide grains that can be uniformly (non-imagewise) developed irrespective of unexposed portions and exposed portions of the photosensitive material. A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.7.
5 μm, particularly preferably 0.05 to 0.6 μm, is preferred. Also,
The grain shape is not particularly limited, and may be regular grains or polydispersed emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the development process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of the equivalent circle diameter of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains is
There is no need for optical sensitization, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. The coated silver amount of the light-sensitive material of the present invention is preferably not more than 6.0 g / m ² , and is 4.5.
g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1 Chemical sensitizer page 23, page 648, right column, page 866 2 Sensitivity enhancer, page 648, right column 3 Spectral sensitizer, page 23-24, page 648, right column 866-868 Super sensitization 〜49 right column 4 Brightener 24 page 868 5 Antifoggant 24-25 page 649 right column 868-870 and stabilizer 6 light absorber, 25-26 page 649 right column-873 filter Dye 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 page left column 872 to right column 8 Dye image stabilizer 25 page 650 page left column 872 9 hardener 26 page 651 left column 874 to Page 875 10 Binder page 26 Same as above 873 to 874 11 Plasticizers and lubricants page 27 650 right side column 876 page 12 Coating aids, page 26 to 27 Same as above 875 to 876 Surfactant 13 Static prevention page 27 Same as above 876 to 876 Page 877 Stopper 14 Matting agent 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of reacting with formaldehyde described in JP-A No. 87 or 4,435, 503 and immobilizing the same to the light-sensitive material. In the light-sensitive material of the present invention, U.S. Patent Nos. 4,740,454 and 4,788,132 are used.
JP-A-62-18539, JP-A-1-28355
It is preferable to include the mercapto compound described in No. 1 above. Compounds which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing described in JP-A-1-106052. Is preferably contained. The light-sensitive material of the present invention may be added to International Publication WO88 / 04.
Nos. 794 and 317, 308A, U.S. Pat. No. 4,420,555, and JP-A-1-259358.
It is preferable to include the dye described in (1).

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure (RD) Nos. 17643, VII-CG and VII-CG and Nos. 307105 and VII-C. To the patents listed in G. As the yellow coupler, for example, U.S. Pat. Nos. 3,933,501 and 4,022,6
No. 20, No. 4,326,024, No. 4,401,
No. 752, No. 4,248,961, No. 58-1
No. 0739, British Patent Nos. 1,425,020 and 1,476,760, US Pat. No. 3,973,968
No. 4,314,023, No. 4,511,64
No. 9, EP 249,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795 are particularly preferable.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred. Further, JP-A-64-553 and JP-A-64-5
Nos. 54, 64-555 and 64-556, and pyrazoloazole couplers described in U.S. Pat.
No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusivity include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent No. 3 (published). , 234,533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
VII-G of 17643, VII-G of No. 307105
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120 as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, Section VII-F and No. 307105, VII-
Patent described in section F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

The bleaching accelerator releasing couplers described in RD Nos. 11449 and 24241 and JP-A-61-201247 are effective for shortening the time of the processing step having bleaching ability. The effect is great when it is added to a light-sensitive material using silver halide grains.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a leuco dye releasing coupler described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Emitting couplers and the like.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027, etc. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-t-amylphenol etc.), aliphatic 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-octyl aniline, etc.) Hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene), and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
In the color light-sensitive material of the present invention, phenethyl alcohol and JP-A-63-257747 and JP-A-62-272248 are used.
And JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol,
It is preferable to add various preservatives or fungicides such as (4-thiazolyl) benzimidazole.

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 described in RD. No. 17643, page 28, and No. 18
No. 716, from the right column on page 647 to the left column on page 648;
07105, page 897. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and 23 μm or less.
Or less, more preferably 18 μm or less,
Particularly preferably, it is 16 μm or less. Also, the film swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Phot) by A. Green et al.
ogr. Sci Eng.), 19 vol., No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. with a color developer, 1/3
90% of the maximum swollen film thickness reached when the treatment is performed for 5 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a hardener to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the following formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention preferably has a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer,
It is preferable to include a lubricant, a coating aid, a surfactant and the like. The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. 17643, pp. 28-29, No. 18
716, pages 880 to 881 of No. 307105.

The color developing solution used for the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N-diethylaniline, 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-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor or an antifoggant such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, ethylene glycol, diethylene glycol Organic solvents such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenediamine Acetic 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'-
Tetramethylene phosphonic acid, ethylenediamine-di (o
-Hydroxyphenylacetic acid) and their salts.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. A known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone in the black-and-white developer. Alternatively, they can be used in combination. The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment solution and air (cm ² )] ÷ [capacity of treatment solution (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.1% or less. 001 to 0.05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, Japanese Patent Application Laid-Open No.
No. 033, a method using a movable lid,
And a slit developing method described in JP-A-216050. Reducing the aperture ratio is
It is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps such as bleaching, bleach-fixing, fixing, washing and stabilization. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

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. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Representative bleaching agents include organic complex salts of iron (III) such as amino diamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are preferred 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 the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be performed at a lower pH in order to speed up the processing. .

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715; iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30;
Polyamine compounds described in JP-A-5-8836; and JP-A-49-40943, JP-A-49-59644 and JP-A-53-96444
No. 94927, No. 54-35727, No. 55-265
Nos. 06 and 58-163940; bromide ions and the like. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
Are preferred. Further, U.S. Pat.
Compounds described in 552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pka) of 2 to 5, specifically acetic acid,
Propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, an adduct of carbonyl bisulfite, or a sulfinic acid compound described in European Patent No. 294,769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, It is preferable to add imidazoles such as methyl imidazole in an amount of 0.1 to 10 mol / l.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 minute to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method of strengthening the stirring include a method described in JP-A-62-183460, in which a jet of a processing solution is caused to impinge on the emulsion surface of a light-sensitive material.
No. 183461, a method of increasing the stirring effect by using the rotating means, and furthermore, by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and making the emulsion surface turbulent, the stirring effect is improved. And a method of increasing the circulating flow rate of the entire processing liquid. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator.

The automatic developing machine used for processing the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-60-19.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. Japanese Unexamined Patent Publication No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a transport means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

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 step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Vol. 64, p. 248-
253 (May, 1955).

According to the multistage countercurrent method described in the above document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. 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 JP-A-62-288838 can be used very effectively. Also, Japanese Patent Application Laid-Open No.
No. 8542, isothiazolone compounds, thiabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles. "Sterilization, Sterilization, and Mold Prevention Technology of Microorganisms" edited by the Sanitation Technology Society (1982
The fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986), edited by the Japan Society of Bacteria and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, and the like, but are generally in the range of 15 to 45 ° C for 20 seconds to 10 minutes, preferably in the range of 25 to 40 ° C for 30 seconds to 5 minutes. Is done. Further, the light-sensitive material of the present invention may be replaced with the above-mentioned water washing,
It can also be treated directly with a stabilizing solution. In such a stabilization process, JP-A-57-8543 and JP-A-5-8543 describe the same.
All known methods described in JP-A Nos. 8-14834 and 60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde bisulfite adducts. Various chelating agents and fungicides can be added to the stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
Nos. 342,597; 3,342,599; Schiff base compounds described in Research Disclosure Nos. 14850 and 15159; and aldol compounds described in No. 13924. And metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
No. 4547 and No. 58-115438.

Various processing solutions in the present invention may be used at a temperature of 10 ° C to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, 59-218443, 61-23805
No. 6, EP 210,660 A2 and the like.

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Next, the present invention will be described in more detail with reference to examples.

Example 1 On an undercoated cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g / m ² of silver for silver halide and colloidal silver, and g / m ^{2 for} couplers, additives and gelatin.
Amounts expressed in m ² units and, for sensitizing dyes, the number of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there is more than one utility, only one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 2.33 ExM-2 0.11 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ⁻² Solv-1 0.16 Solv-2 0.10 ExF-1 1.0 × 10 ⁻² ExF-2 4.0 × 10 ⁻² ExF-3 5.0 × 10 ⁻³ Cpd -6 1.0 x 10 ^-3

Second Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 30%, plate-like grain , Diameter / thickness ratio 3.0) coating amount of silver 0.35 silver iodobromide emulsion (AgI 6.0 mol%, core / shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.45 μm, sphere equivalent diameter Coefficient of variation 23%, plate-like particles, diameter / thickness ratio 2.0) Silver coating amount 0.18 Gelatin 0.77 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.3 × 10 ⁻⁴ ExS-7 4.1 × 10 ⁻⁶ ExC-1 0.09 ExC-2 4.1 × 10 ⁻² ExC-3 8.0 × 10 ⁻² ExC-5 0.08

Third Layer (Medium Speed Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 6.0 mol%, core-shell ratio 1: 2, high internal AgI type, equivalent sphere diameter 0.65 μm, variation in equivalent sphere diameter) Coefficient 23%, plate-like particles, diameter / thickness ratio 2.0) coated silver amount 0.80 gelatin 1.46 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2 .4 × 10 ⁻⁴ ExS-7 4.3 × 10 ⁻⁶ ExC-1 0.19 ExC-2 2.0 × 10 ⁻² ExC-3 0.10 ExC-5 0.19 ExC-6 2.0 × 10 ^-2 ExM-3 2.0 × 10 ^-2 UV-2 5.7 × 10 ^-2 UV-3 5.7 × 10 ^-2

Fourth Layer (High-Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI: 9.3 mol%, core-shell ratio: 3: 4: 2, multi-structure grains, 24, 0, 6 mol from the inside of AgI content) %, Equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particle, diameter / thickness ratio 2.5) Silver coating amount 1.49 Gelatin 1.38 ExS-1 2.0 × 10 ^-4 ExS-2 1.1 × 10 ^-4 ExS-5 1.9 × 10 ^-4 ExS-7 1.4 × 10 ^-5 ExC-1 8.0 × 10 ^-2 ExC-4 9.0 × 10 ^-2 ExC-6 2.0 × 10 ^-2 Solv-1 0.20 Solv-2 0.53

Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ⁻² Solv-1 8.0 × 10 ⁻²

Sixth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.33 μm, variation coefficient of sphere equivalent diameter 37%, plate-like particles , Diameter / thickness ratio 2.0) amount of coated silver 0.19 gelatin 0.44 ExS-3 1.5 × 10 ^-4 ExS-4 4.4 × 10 ^-4 ExS-5 9.2 × 10 ^-5 ExM -1 0.17 ExM-3 3.0 × 10 ^-2 Solv-1 0.13 Solv-4 1.0 × 10 ^-2

Seventh Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 15%, plate-like particles , Diameter / thickness ratio 4.0) amount of coated silver 0.24 gelatin 0.54 ExS-3 2.1 × 10 ^-4 ExS-4 6.3 × 10 ^-4 ExS-5 1.3 × 10 ^-4 ExM -1 0.15 ExM-3 4.0 × 10 ^-2 ExY-1 3.0 × 10 ^-2 Solv-1 0.13 Solv-4 1.0 × 10 ^-2

Eighth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 8.8 mol%, multi-structured grains having a silver amount ratio 3: 4: 2, AgI content of 24, 0, 3 from the inside). Mol%, equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter / thickness ratio 1.6) Coating silver amount 0.49 Gelatin 0.61 ExS-4 4.3 × 10 ^{− 4} ExS-5 8.6 × 10 ⁻⁵ ExS-8 2.8 × 10 ⁻⁵ ExM-2 2.0 × 10 ⁻² ExM-5 2.0 × 10 ⁻² ExM-6 6.0 × 10 ^{− 2} ExY-1 3.0 × 10 ^-2 ExC-1 0.8 × 10 ^-2 ExC-4 0.5 × 10 ^-2 ExC-6 1.0 × 10 ^-2 Solv-1 0.23 Solv-2 5.0 × 10 ^-2 Solv-4 1.0 × 10 ^-2 Cpd-8 1.0 × 10 ^-2

Ninth layer (intermediate layer) Gelatin 0.56 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2 UV-4 ^{0x10 -2} UV-5 4.0x10 ^-2

Tenth layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 8.0 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.65 μm, sphere equivalent) Coefficient of variation of diameter 25%, tabular grains, diameter / thickness ratio 2.0) Silver coating amount 0.67 Silver iodobromide emulsion (AgI 4.0 mol%, core-shell ratio 1: 3, internal high AgI type, sphere) (Equivalent diameter 0.4 μm, sphere equivalent diameter variation coefficient 15%, normal crystal grains) Silver coating 0.20 Gelatin 0.87 ExS-3 6.7 × 10 ^-4 ExM-4 0.16 Solv-1 30 Solv-6 3.0 x 10 ^-2

Eleventh layer (yellow filter layer) Yellow colloidal silver 9.0 × 10 ^-2 gelatin 0.84 Cpd-2 0.13 Solv-1 0.13 Cpd-1 8.0 × 10 ^-2 Cpd-6 2.0 x 10 ^-3 H-1 0.25

Twelfth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grains , Diameter / thickness ratio 7.0) Silver coated amount 0.50 Silver iodobromide emulsion (AgI 3.0 mol%, uniform AgI type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 30%, plate shape Grain, diameter / thickness ratio 7.0) Coating silver amount 0.30 Gelatin 2.18 ExS-6 9.0 × 10 ^-4 ExC-1 0.05 ExC-2 0.10 ExY-2 0.05 ExY- 3 1.09 Solv-1 0.54

Thirteenth Layer (Intermediate Layer) Gelatin 0.40 ExY-4 0.19 Solv-1 0.19

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter 1.0 μm, variation coefficient of equivalent spherical diameter 25%, multiplex Crystal plate-shaped particles, diameter / thickness ratio 2.0) Silver coating amount 0.40 Gelatin 0.49 ExS-6 2.6 × 10 ^-4 ExY-2 1.0 × 10 ^-2 ExY-3 0.20 ExC -1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2

Fifteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Silver coating amount 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Solv-5 2.0 × 10 ^-2 Cpd-5 0.10 Polyethyl acrylate latex 9.0 × 10 ^-2

Sixteenth Layer (Second Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.85 B-1 (1.5 μm in diameter) 8.0 × 10 ⁻² B-2 (1.5 μm in diameter) 8.0 × 10 ⁻² B-3 2.0 × 10 ⁻² W-4 2.0 × 10 ⁻² H -1 0.18

The samples prepared in this manner include, in addition to the above,
1,2-Benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. B-4, B-5, F-1, F-2, F-3,
F-4, F-5, F-6, F-7, F-8, F-9, F
-10, F-11, F-12 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

In each layer, in addition to the above components, a surfactant W
-1, W-2 and W-3 were added as coating aids and emulsifying dispersants.

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(Samples 102 to 110) First Sample 101
Samples 102 to 110 were prepared in the same manner as Sample 101, except that the compound ExM-4 in the 0 layer was changed as shown in Table 1.

After subjecting the obtained Samples 101 to 110 to white imagewise exposure, using an automatic developing machine, the following method (until the cumulative replenishment amount of the liquid becomes three times the mother liquor tank capacity) was carried out. Development processing was performed.

Treatment method Process treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C. 33 ml 20 liters Bleach 6 minutes 30 seconds 38 ° C. 25 ml 40 liters Water washing 2 minutes 10 seconds 24 ° C. 1200 ml 20 liters Fixed arrival 4 Minutes 20 seconds 38 ℃ 25ml 30 liters Water wash (1) 1 minute 05 seconds 24 ℃ 10 liters from (2) to (1) Countercurrent piping water wash (2) 1 minute 00 seconds 24 ℃ 1200ml 10 liters Stability 1 minute 05 seconds 38 ℃ 25ml 10 liters Dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m per length

Next, the composition of the processing solution will be shown. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2 -Methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.10

(Bleach) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 10.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Water was added to 1.0 liter 1.0 liter pH 6.0 5.7

(Fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Aqueous ammonium thiosulfate solution (70 %) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 liter pH 6.7 6.6

(Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediamine Acetic acid disodium salt 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0

Table 1 shows the MTF value of the magenta image of the obtained sample at 25 cycles / mm. MTF values are measured by Theory of the Photographic Process, 3rd e
d. The method described in (Mcmillan, Mies) was used. Further, after giving a blue uniform exposure, a green image-like exposure is given, and the value obtained by subtracting the yellow density in the magenta fog density from the yellow density in the exposure amount giving the magenta density (fog + 1.2) is the color turbidity (ΔD _B ) is shown in Table 1.

Further, the same sample was simultaneously exposed to white images two by two, one of which was stored in a freezer at 50 ° C. and a relative humidity of 80% for 7 days, and subjected to the same developing treatment as described above. Then, the change in sensitivity at the point of magenta density (fog + 0.5) was read, and the sensitivity of the light-sensitive material (ΔS _0.5 ) was measured as shown in Table 1.
It was shown to. Here, the change in sensitivity is the density (fog + 0.5)
Exposure before and after storage, respectively.
_It was expressed by logE ₀ −logE ₁ when ₀ and E ₁ .

Further, the sample after the development processing was placed on a fluorescent lamp 2000
It was stored under the condition of 0 Lux for 7 days, and the change in density at the point of magenta density (fog + 1.0) was read. The results are shown in Table 1 together with the light fastness (ΔD _G ).

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[Table 1]

As is clear from Table 1, the sample using the compound of the present invention is excellent in sharpness represented by MTF value and color reproducibility represented by color turbidity. Further, it can be seen that the sample of the present invention is more excellent in the preservability of the light-sensitive material, and in particular, the light fastness is remarkably improved.

Example 2 On an undercoated cellulose triacetate film support,
A sample 201, which is a multilayer color photosensitive material composed of each layer having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g / m ² of silver for silver halide and colloidal silver, and g / m ^{2 for} coupler, additive and gelatin.
The amount was expressed in m ² , and the sensitizing dye was expressed in moles per mole of silver halide in the same layer.

First Layer: Antihalation Layer Black Colloidal Silver Silver Coating Amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1. 9 × 10 ^-2 Solv-1 0.30 Solv-2 1.2 × 10 ^-2

Second layer: Intermediate layer Fine grain silver iodobromide (AgI 1.0 mol%, equivalent sphere diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2 Cpd -3 2.0 x 10 ^-2

Third Layer: First Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high Ag1 type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains , Diameter / thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high Ag1 type, sphere equivalent diameter 0.4 μm, sphere equivalent diameter variation coefficient 18%, 10 Tetrahedral grains) Silver coating amount 0.40 Gelatin 1.90 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.0 × 10 ^-5 mol ExC- 1 0.65 ExC-3 1.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 Solv-1 0.32

Fourth Layer: Second Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high Agl type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles , Diameter / thickness ratio 3.0) Silver coating amount 0.85 Gelatin 0.91 ExS-1 3.0 × 10 ⁻⁴ mol ExS-2 1.0 × 10 ⁻⁴ mol ExS-3 3.0 × 10 ^{− 5} mol ExC-1 0.13 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 ExC-6 3.0 × 10 ^-2 Solv-1 0.10

Fifth Layer: Third Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high Ag1 type, sphere equivalent diameter 1.4 μm, sphere equivalent diameter variation coefficient 28%, tabular grains , Diameter / thickness ratio 6.0) Silver coating amount 1.50 Gelatin 1.20 ExS-1 2.0 × 10 ⁻⁴ mol ExS-2 6.0 × 10 ⁻⁵ mol ExS-3 2.0 × 10 ^{− 5} mols ExC-2 5.0 × 10 ^-2 ExC-4 7.3 × 10 ^-2 ExC-6 1.0 × 10 ^-2 ExC-7 4.0 × 10 ^-2 Solv-1 0.12 Solv- 2 0.12

Sixth Layer (Intermediate Layer) Gelatin 1.00 Cpd-4 8.0 × 10 ⁻² Solv-1 8.0 × 10 ⁻²

Seventh Layer: First Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent spherical diameter of 0.9 μm, coefficient of variation of equivalent spherical diameter of 21%, tabular grains , Diameter / thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high Ag1 type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 18%, 10 Tetrahedral grains) Silver coating amount 0.16 Gelatin 1.20 ExS-4 5.0 × 10 ^-4 mol ExS-5 2.0 × 10 ^-4 mol ExS-6 1.0 × 10 ^-4 mol ExM- 1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 ^-2 Solv-1 0.20 Solv-3 3.0 × 10 ^-2

Eighth Layer: Second Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high Agl type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles , Diameter / thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.45 ExS-4 3.5 × 10 ⁻⁴ mol ExS-5 1.4 × 10 ⁻⁴ mol ExS-6 7.0 × 10 ^{− 5} mol ExM-1 0.12 ExM-2 9.0 × 10 ⁻³ ExM-3 3.5 × 10 ⁻² Solv-1 0.15 Solv-3 1.0 × 10 ⁻²

Ninth layer: Intermediate layer Gelatin 0.50 Solv-1 2.0 × 10 ⁻²

Tenth Layer: Third Green-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high Ag1 type, sphere equivalent diameter 1.4 μm, sphere equivalent diameter variation coefficient 28%, tabular grains , Diameter / thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20 ExS-4 2.0 × 10 ⁻⁴ mol ExS-5 8.0 × 10 ⁻⁵ mol ExS-6 8.0 × 10 ^{− 5} mol ExM-4 5.8 × 10 ⁻² ExM-6 5.0 × 10 ⁻³ ExC-2 4.5 × 10 ⁻³ Cpd-5 1.0 × 10 ⁻² Solv-1 0.25

Eleventh layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ⁻² Solv-1 0.12

Twelfth layer: intermediate layer Gelatin 0.45 Cpd-3 0.10.

13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grains, diameter / Thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ⁻⁴ mol ExY-1 0.60 ExY-2 2.3 × 10 ⁻² Solv-1 0.15

Fourteenth Layer: Second Blue-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high Ag1 type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 16%, octahedral grains ) Silver coating amount 0.19 Gelatin 0.35 ExS-7 2.0 × 10 ⁻⁴ mol ExY-1 0.22 ExY-3 1.0 × 10 ⁻³ Solv-1 7.0 × 10 ⁻²

Fifteenth layer: intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform Agl type, sphere equivalent diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36

Sixteenth Layer: Third Blue Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, spherical equivalent diameter 1.7 μm, variation coefficient of spherical equivalent diameter 28%, plate-like particles , Diameter / thickness ratio 5.0) Silver coating amount 1.40 Gelatin 1.00 ExS-8 1.5 × 10 ^-4 mol ExY-1 0.21 Solv-1 7.0 × 10 ⁻²

17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 Solv-1 1.0 × 10 ^-2 Solv-2 1.0 × 10 ^-2

18th layer: 2nd protective layer Fine particle silver chloride (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (1.5 μm diameter) 2.0 × 10 ^-2 B- 2 (1.5 μm diameter) 0.15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00

In addition to the above, the samples thus prepared were
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. Further, B-4, B-5, W-2, W-3, F-1,
F-2, F-3, F-4, F-5, F-6, F-7, F
-8, F-9, F-10, F-11, F-12, F-1
3 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt.

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(Samples 202 to 210) Seventh Sample 201
Samples 202 to 210 in the same manner as Sample 201 except that the compound ExM-2 of the layer and the eighth layer was changed as shown in Table 2.
Was prepared.

According to Example 1, the color turbidity (ΔD _B ) of the obtained sample, the storage stability of the photosensitive material (ΔS _0.5 ), and the light fastness (ΔD)
_G ) was determined and is shown in Table 2. Table 2 also shows the RMS values at the magenta density (fog + 1.0) measured with an aperture having a diameter of 48 μm.

However, the color development processing was performed in the processing steps and processing liquid compositions shown below. Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ° C 25 ml 10 liters Bleaching 45 seconds 38 ° C 5 ml 4 liters Fixed (1) 45 seconds 38 ° C -4 liters Fixed (2) 45 seconds 38 ℃ 30 ml 4 liters Water wash (1) 20 seconds 38 ℃ -2 liters Water wash (2) 20 seconds 38 ℃ 30 ml 2 liters Stability 20 seconds 38 ℃ 20 ml 2 liters Dry 1 minute 55 ℃ Replenishment amount is 35mm Amount per 1 m width Each of the bleach-fixing and water-washing steps is a countercurrent method from (2) to (1), and the overflow of the bleaching solution is all introduced into the bleach-fixing (2). In the above processing, the amount of the bleach-fixing solution brought into the washing step was 35 mm wide photosensitive material 1.
It was 2 ml per m.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 3.0. 5 Potassium iodide 1.2 mg-Hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.7 4.7 6.2 Add water 1.0 liter 1.0 liter pH10.00 10.15

(Bleach) Mother liquor (g) Replenisher (g) 1,3-Diaminopropanetetraacetic acid Ferric ammonium monohydrate 144.0 206.0 1,3-Diaminopropanetetraacetic acid 2.8 4. 0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Aqueous ammonia (27%) 10.0 1.8 Acetic acid (98%) 51.1 73.0 Add water 1.0 liter 1.0 liter pH 4 3.3 3.4

(Bleach-fixing solution) Mother liquor (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 25.0 Ammonium sulfite 12.0 20. 0 Ammonium thiosulfate aqueous solution (70 g / liter) 290.0 ml 320.0 ml ammonia water (27%) 6.0 ml 15.0 ml water was added to add 1.0 liter 1.0 liter pH 6.8 8.0

(Washing water) Common to mother liquor and replenisher tap water was prepared using H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-). 4
00) to reduce the concentration of calcium and magnesium ions to 3 mg / liter or less, followed by 20 m of sodium diisocyanurate dichloride.
g / L and 150 mg / L of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Surfactant [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] 0.4 Ethylene Glycol 1.0 Add water 1.0 liter pH 5.0-7.0

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[Table 2]

As is clear from Table 2, the sample using the compound of the present invention is excellent in granularity represented by RMS value and color reproducibility represented by color turbidity. Further, it can be seen that the sample of the present invention is excellent in the storability of the light-sensitive material, and further, the light fastness after processing is remarkably improved.

[0246]

The silver halide color photographic light-sensitive material of the present invention is excellent in sharpness, granularity and color reproducibility due to the improvement of the layering effect, and is also particularly excellent in photographic material storage stability and light fastness after processing. There is.

Claims (1)

(57) [Claims] 1. A silver halide color photographic material comprising a development inhibitor releasing coupler represented by the following general formula (I). Embedded image (In the formula, R ₁ and R ₂ represent an aliphatic group or an aromatic group, and R ₃ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a hydroxyl group,
An alkoxy group, an aryloxy group, a heterocyclic oxy group,
Acyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carbamoyloxy, sulfamoyloxy, sulfonyloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, amino, anilino, hetero Ring amino group, amide group, alkoxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, azo group, nitro group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group, sulfonyl group, sulfamoyl group , Sulfo group and phosphinyl group, and n represents an integer of 0 to 3. Z ₁ and Z ₂ are each independently, = N-or = C (R ₄₎ - represents,
R ₄ has the same meaning as R ₃ . When Z ₁ and Z ₂ are both = C (R ₄ )-, two R ₄ may be the same or different. R _{1 to} R ₄ may form a bis form with a divalent group. DI represents a development inhibitor residue. )