JPH0690466B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material excellent in sharpness, graininess and color reproducibility.

(Prior Art) In recent years, in silver halide photographic light-sensitive materials, especially photographic light-sensitive materials, ultra-high-sensitivity light-sensitive materials typified by ISO1600 film and typified by 110-size cameras and disk cameras There is a demand for a photosensitive material having a high image quality and a high sharpness suitable for a small-format camera.

Conventionally, as one of means for improving sharpness and graininess, a compound (hereinafter referred to as a DIR compound) which releases a development inhibitor corresponding to the density of an image during development is contained in a halogen silver color photographic light-sensitive material. It is known.

This DIR compound is generally of a type that releases a development inhibitor by reacting with an oxidation product of an aromatic primary amine developing agent. As a typical example, the coupler is separated from the coupling position to the coupling position of the coupler. A group that forms a compound having a development inhibitory action when introduced is a so-called DIR coupler (for example, US Pat. Nos. 3,227,554 and 3,701,783).
No. 4,095,984, 4,149,886, 3,933,500,
Compounds described in Nos. 4,146,396 and 4,477,563 are known. This is a compound in which the coupler base forms a dye while undergoing a coupling reaction with the oxidation product of an aromatic primary amine developing agent, while releasing a development inhibitor.

Also, as a compound which forms a colorless dye by coupling reaction with an oxidized product of an aromatic primary amine developing agent, while releasing a development inhibitor, for example, U.S. Pat. No. 3,632,34
No. 5, No. 3,928,041, No. 3,958,993, No. 3,961,959,
The compounds described in JP-A-4,052,213, JP-A-53-110,529, JP-A-54-13333 and the like are known.

Further, as a so-called DIR hydrokin that releases a development inhibitor by a cross-oxidation reaction with an oxidized product of a developing agent,
For example, they are known as compounds described in US Pat. Nos. 3,379,529 and 3,930,863.

However, these compounds have drawbacks such as deterioration of function due to decomposition during coating and storage of the film after coating, desensitization and the like, and the effect of improving the sharpness is not sufficient, so that improvement of the sharpness is not sufficient. It was not there.

Further, as a compound which releases a development inhibitor with a timing of a leaving group when it is coupled with an oxidized product of an aromatic primary amine developing agent, for example, US Pat.
They are disclosed as compounds described in 962 and JP-A-57-56837.

Certainly, when this type of compound is used, it is possible to exert the effect of the inhibitor at a position separated from the developed silver halide grain by a specific distance, so the sharpness should be improved based on the so-called adjacent effect. However, since the timing of these compounds is not sufficient, the improvement in sharpness was not sufficient. Further, there is a problem that hydrolysis or cleavage is inevitable during storage of the film in a high humidity condition, which causes desensitization or deterioration of its function.

To solve these problems, Japanese Patent Application No. 59-33059
It has been proposed that a compound released after a coupling reaction with an oxidized product of a developing agent undergoes a redox reaction with an oxidized product of another developing agent to release a photographically useful group such as a development inhibitor.

Certainly, a photographic material containing a compound which finally releases a development inhibitor among these compounds was excellent in storage stability, and the sharpness was remarkably improved. However, when a large amount is used with respect to silver halide in an emulsion layer containing these compounds, its development inhibiting effect is too large, sensitivity is remarkably lowered, gradation control becomes extremely difficult, and an oxidation product of a developing agent is generated. A group capable of reacting with another molecule of the developing agent oxidant, which is released by the reaction, exerts an adverse effect to desensitize, and sharpness is improved by the undesired adjacent developing effect of the portion reacting with the developing agent oxidant. It has become clear that it has the drawback of making things worse.

On the other hand, as a compound obtained by removing the development inhibitor moiety from the compound of the present invention, partially similar compounds are described in JP-A-57-138636 and US Pat. No. 4,477,560. These compounds are
The present invention is completely different from the present invention in that the split off part acts as a component for scavenging the oxidant of the color developing agent, and therefore, it is completely different from the present invention.
As claimed in the publication, the effect is exhibited only when the addition amount in the highest sensitivity layer is added. However, the compounds of the present invention exhibit a sufficient effect even when added to a silver halide emulsion layer other than the highest sensitivity.

(Object of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in sharpness, graininess and color reproducibility.

(Structure of the Invention) The object of the present invention is to provide a silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, A compound in which at least one light-sensitive layer is composed of two or more layers having different sensitivities and (a) is oxidized to a silver halide emulsion layer other than the highest sensitivity layer to form a development inhibitor or a precursor thereof. Generated by reaction with oxidized form of developing agent (b)
A compound represented by the following general formula (I), which is formed by reacting a development inhibitor or a precursor of a compound which is not oxidized only with an oxidized product of a developing agent, to a silver halide in the photosensitive layer. And a silver halide color photographic light-sensitive material characterized by containing at most 5 mol%.

Two or more compounds of the present invention may be used in combination, and the same compound may be used in layers other than the silver halide emulsion layer other than the highest sensitivity layer (for example, the highest sensitivity silver halide emulsion layer, substantially the same color-sensitive layer). It may be added to a non-photosensitive emulsion layer which is adjacent to a silver halide emulsion layer having different sensitivities at the same time.

The compound of the present invention is added to a silver halide emulsion layer other than the highest sensitive layer of the silver halide emulsion layers having substantially the same color sensitivity and different sensitivities of the silver halide color photographic light-sensitive material. The addition amount is at most 5 mol% per 1 mol of silver halide of the silver halide agent in the same layer, and if the addition amount is more than this, problems such as desensitization, softening and deterioration of sharpness become remarkable. As an addition amount, per mol of silver halide,
Preferably from 0.005 mol% to 3 mol%, more preferably
0.01 mol% to 2 mol%, more preferably 0.05 mol%
To 1 mol%.

The color-sensitive silver halide emulsion layer to which the compound of the present invention is added requires at least two silver halide emulsion layers, which may or may not be adjacent to each other. Further, these two layers may be further divided into layers having different sensitivities. Further, a non-color sensitive layer may be provided adjacent to these two layers at the same time.

In formula (I) A-B-D, A represents a coupler residue that cleaves the bond between A and B upon reaction with an oxidized product of a developing agent, and B is oxidized after the bond between A and C is cleaved. Represents a group that cleaves the bond between B and D or a precursor thereof, and D represents a development inhibitor or a precursor thereof.

In the general formula (I), B is preferably the following general formula (B
-1). Here, the * mark represents the position of binding to A, and the ** mark represents the position of binding to D.

General formula (B-1) In the formula, B ₁ represents a linking group which cleaves the bond between B ₁ and RED after the bond between B ₁ and A is cleaved, and B ₂ reacts with alkali, hydroxylamine, or sulfite ion present during development. Represents a group in which the bond with RED is cleaved, and RED has a structure that is oxidized only after the bond with B ₁ and B ₂ is cleaved, and is oxidized to be D (as described in the general formula (I)). (Same meaning) and a group that cleaves the bond between RED and v and w each represent 0 or 1.

In the formula, the group represented by RED is preferably the following general formula (R
-1). Here, the * mark is A- (B ₁ )
_It represents the position of bonding to _v −, and the ** mark represents the position of bonding to B ₂ (when w = 1) or a hydrogen atom (when w = 0).

General formula (R-1) * -PX = Y _n Q-** In the formula, P and Q represent an oxygen atom or a substituted or unsubstituted imino group, and at least one of n X and n Y Represents a methine group having D (D has the same meaning as defined in formula (I)) as a substituent,
Other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n represents an integer of 1 to 3. When n is 2 or more, n Xs and n Ys are the same or different. Where R, X, Y and Q
It also includes the case where any two substituents are combined with a divalent group to form a cyclic structure.

In the general formula (B-1), B ₁ is preferably the following.

(1) A group that utilizes a cleavage reaction of hemiacetal. For example, U.S. Pat. Nos. 4,146,396, Japanese Patent Application Nos. 59-106223 and 59-106.
No. 224 and No. 59-75475, and a group represented by the following general formula. Here, the * mark represents the position of binding to A, and the ** mark represents the position of binding to RED.

In the formula, W is an oxygen atom or (R ₃ represents an organic substituent), R ₁ and R ₂ represent a hydrogen atom or a substituent, t represents 1 or 2, and when t is ₂ , each of _two R ₁ and R ₂ is _They may be the same or different, and include the case where any _{two of} R ₁ , R ₂ and R ₃ are linked to form a cyclic structure.

When R ₁ and R ₂ represent a substituent, a typical substituent is an acyl group (eg benzoyl group, acetyl group), a carbamoyl group (eg N-ethylcarbamoyl group, N-phenylcarbamoyl group) or an aliphatic group ( For example, a methyl group and a butyl group). The group represented by R ₃ is, for example, an acyl group (eg acetyl group, benzoyl group), a sulfonyl group (eg methanesulfonyl group, benzenesulfonyl group), an aliphatic group (eg methyl group, ethyl group) or a carbamoyl group (eg ethylcarbamoyl). Group, a phenylcarbamoyl group). Typical examples of the case where any of R ₁ , R ₂ and R ₃ are linked to form a cyclic structure include the following.

In the formula, R ′ ₁ is preferably an aliphatic group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, butyl group) or hydrogen atom.

(2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction. For example, the timing groups described in US Pat. No. 4,248,962.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system. For example, a group described in US Pat. No. 4,409,323 or a group represented by the following general formula (UK group 2,096,783A)).

In the formula, * indicates the position of binding to A, and ** indicates RED
And R ₄ and R ₅ represent a hydrogen atom or a substituent.

When R ₄ represents a substituent, it is preferably an aliphatic group (eg, methyl group, benzyl group) or aromatic group (eg, phenyl group, 2,4,6-trichlorophenyl group). When R ₅ represents a substituent, preferably an aliphatic group (for example, a methyl group,
It is an ethyl group), an aromatic group (for example, a phenyl group, a 4-methoxyphenyl group) or an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group).

In the general formula (B-1), B ₂ represents a group which is cleaved at a bond with RED by reacting with a nucleophile such as hydroxylamine or sulfite ion present in an alkali or a developing solution.
Preferably, a hydrolyzable group such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxazoyl group and a sulfonyl group,
U.S. Patent No. 4,009,029 type precursor group utilizing a reverse Michael reaction, U.S. Pat.No. 4,310,612 after ring-cleavage reaction, a precursor group of a type utilizing the generated anion as an intramolecular nucleophilic group, U.S. Pat.No. 3,674,
No. 478, No. 3,932,480 or No. 3,993,661, an anion described in US Pat. No. 4,335,200 by an electron transfer of the anion generated after the ring cleavage described in U.S. Pat. Precursor group that causes cleavage reaction, or US Pat.
Precursor groups utilizing an imidomethyl group described in 4,363,865 and 4,410,618 are mentioned.

In the general formula (B-1), v is 0 and w is preferably 0.

In the general formula (I), D is preferably the following general formula (D-
1). Here, the * mark represents the position where B is bonded.

In the formula _{(D-1) * B 1} ) q -DI formula, B ₁ is the general formula (B-1) represent the same meaning as defined for, q is 0 or 1, DI is a development inhibitor Represents

DI is preferably a tetrazolylthio group, 1 or 2-benzotriazolyl group, 1-benzoindaryl group, benzimidazolylthio group, benzoxazolylthio group, imidazolylthio group, oxazolylthio group, triazolylthio group, oxadiazolylthio group, Examples thereof include a thiadiazolylthio group or an N-aryl-1,2,3,4-thiatriazole-5-amino group. Where N-aryl-1,
The 2,3,4-thiatriazole-5-amino group does not itself have a development inhibitory effect (after being cleaved), but undergoes a rearrangement reaction to produce 5-mercapto-1-phenyltetrazole and exert an inhibitory effect. (This is a reaction described in West German Published Patent No. 3,307,506A). The development inhibitors listed above may have the following substituents at substitutable positions. As the substituent, preferably, an aliphatic group (eg, methyl group, ethyl group, etc.), an aromatic group (eg, phenyl group, 4-chlorophenyl group, etc.), a halogen atom (eg, fluorine atom,
Chloro atom etc.), alkoxy group (eg methoxy group,
Benzyloxy group), alkylthio group (eg ethylthio group, butylthio group), aryloxy group (eg phenoxy group), arylthio group (eg phenylthio group), carbamoyl group (eg N-ethylcarbamoyl group), alkoxycarbonyl group (eg methoxy) Carbonyl group), aryloxycarbonyl group (eg phenoxycarbonyl group), sulfonyl group (eg benzenesulfonyl group, methanesulfonyl group), sulfamoyl group (eg N-ethylsulfamoyl group), acylamino group (eg acetamide group, Benzamide group), sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group), acyl group (eg acetyl group, benzoyl group), nitroso group, acyloxy group (eg acetoxy group), urei A group (for example, a 3-phenylureido group, a 3-ethylureido group), an imide group (for example, a succinimide group), a nitro group, a cyano group, a heterocyclic group (as a hetero atom, a nitrogen atom, an oxygen atom or a sulfur atom, selected from 4 members or 6-membered heterocycle, for example, 2-furyl group, 2-pyridyl group, 1-imidazolyl group, 1-morpholino group), hydroxyl group, carboxyl group, alkoxycarbonylamino group (eg, methoxycarbonylamino group, phenoxy group) Carbonylamino group), sulfo group, amino group, anilino group (for example, 4-methoxyanilino group), aliphatic amino group (for example, diethylamino group), sulfinyl group (for example, ethylsulfinyl group), sulfamoylamino group ( For example, ethylsulfamoylamino group), thioacyl group (eg, phenylthiocarbyl) Group), selected from a thioureido group (e.g., 3-phenylene thioether ureido group) or a heterocyclic amino group (e.g., imidazolylmethyl amino group). When there is an aliphatic group in the partial structure of the substituent, the carbon number is 1 to 22, preferably 1 to 10
And is a linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group. When an aromatic group is contained in the partial structure of the substituent listed above, the number of carbon atoms is 6 to 10, and preferably a substituted or unsubstituted phenyl group.

In general formula (D-1), q is preferably 0.

Particularly preferred couplers in the general formula (I) are those represented by the following general formulas (II) and (III).

General formula (II) General formula (III) In the formula, A and DI have the same meanings as previously defined, Q ₁ represents a hydroxyl group or a sulfonamide group, R ₆ represents a hydrogen atom or a substituent, and a preferred example of the substituent is the general formula ( It is selected from the substituents listed as the substituents for DI in D-1). r represents an integer of 1 to 3. When r is 2 or more, R ₆ represents the same substituent or different substituents. R ₆ is particularly preferably an alkoxy group (for example, a methoxy group, an ethoxy group), a hydroxyl group,
Sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group), acylamino group (eg acetamide group, benzamide group), aliphatic group (eg methyl group, ethyl group) or alkylthio group (eg methylthio group, butylthio group) is there. When two R ₆ 's represent substituents on adjacent carbons, the case where they are linked to each other by a divalent group to represent a cyclic structure is also included. In that case, it becomes a benzene condensed ring, and for example, benzonorbornenes, chromanes, indoles, benzothiophenes, quinolines, benzofurans, 2,3-dihydrobenzofurans,
Examples thereof include indans and indenes.

When Q ₁ represents a sulfonamide group, it is preferably selected from an aliphatic sulfonamide group, an aromatic sulfonamide group or a heterocyclic sulfonamide group. The aliphatic sulfonamide group is specifically a straight-chain or branched, chain-like or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic sulfonamide group having 1 to 20 carbon atoms. The aromatic sulfonamide group is specifically a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms or a substituted or unsubstituted naphthyl group. The heterocyclic group of the heterocyclic sulfonamide group is specifically a 4-membered to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom or an oxygen atom as a hetero atom.

In the general formula (I), A is specifically a yellow coupler residue (open-chain ketomethylene coupler, etc.), a magenta coupler residue (5-pyrazolone, pyrazolotriazole, pyrazoloimidazole, etc.), a cyan coupler residue (phenol, naphthol, etc.). ), And non-color-forming coupler residues (indanone, acetophenone, etc.).

As the yellow coupler mother nucleus, for example, U.S. Pat.
No. 506, No. 2,875,057, No. 3,408,194, JP-A-48-2943
No. 2, No. 48-66834, No. 54-13329, No. 50-87650 and the like, as a magenta coupler nucleus U.S. Patent Nos. 2,600,788, 3,062,653, 3,127,269, 3,4
19,391, 3,519,429, 3,888,680, JP-A-49-1
11631, 59-171956, 59-162548, etc., as cyan coupler mother nucleus U.S. Patent No. 2,474,29
No. 3, No. 2,801,171, No. 3,476,563, No. 4,009,035,
4,333,999, JP-A-50-112038, 50-117422,
55-32071, 53-109630, Research Disclosure (RD) 15741, JP-A-57-204545, and the like. Further, as a mother nucleus of a coupler that does not substantially form a dye, U.S. Patent Nos. 3,958,993 and 3,961,9
Examples include those described in No. 59.

Furthermore, the present invention is particularly effective when A in the general formula (I) is represented by the following general formulas (Cp-1) and (Cp-
2), (Cp-3), (Cp-4), (Cp-5), (Cp-
6), (Cp-7), (Cp-8), (Cp-9), (Cp-1)
0) or a coupler residue represented by (Cp-11). These couplers are preferred because of their high coupling speed.

General formula (Cp-1) General formula (Cp-2) General formula (Cp-3) General formula (Cp-4) General formula (Cp-5) General formula (Cp-6) General formula (Cp-7) General formula (Cp-8) General formula (Cp-9) General formula (Cp-10) General formula (Cp-11) The free bond derived from the coupling position in the above formula represents the coupling position of the coupling-off group. In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R
_{If 59} , R ₆₀ or R ₆₁ contains a diffusion resistant group, it is selected to have a total carbon number of 8 to 32, preferably 10 to 22, otherwise the total number of carbon atoms is 15 or less. preferable.

Next, R _{51 to} R ₆₁ l of the general formulas (Cp-1) to (Cp-11),
The m and p will be described.

In the formula, R ₅₁ represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group, and R ₅₂ and R ₅₃ each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R ₅₁ preferably has 1 carbon atom.
22 to 22 may be substituted or unsubstituted, linear or cyclic. Preferred substituents on the alkyl group are an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom and the like, which may themselves further have a substituent. Specific examples of aliphatic groups useful as R ₅₁ are: isopropyl group, isobutyl group, tert-butyl group, isoamyl group, tert-amyl group, 1,1-dimethylbutyl group, 1,1-dimethylhexyl group, 1,1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group,
2-p-tert-butylphenoxyisopropyl group, α-
Aminoisopropyl group, α- (diethylamino) isopropyl group, α- (succinimide) isopropyl group, α
Examples include-(phthalimido) isopropyl group and α- (benzenesulfonamide) isopropyl group.

When R ₅₁ , R ₅₂ or R ₅₃ represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups are alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, alkylureido groups. , An alkyl-substituted succinimide group or the like may be substituted, in which case the alkyl group may have an aromatic group such as phenylene interposed in the chain. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc. The moiety may be further substituted with one or more alkyl groups having 1 to 22 carbon atoms in total.

The phenyl group represented by R ₅₁ , R _52, or R ₅₃ further includes an amino group, which is substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, It may be substituted with a thiocyano group or a halogen atom.

Further, R ₅₁ , R ₅₂ or R ₅₃ may represent a substituent in which a phenyl group is condensed with another ring, for example, a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group and the like. These substituents may themselves have a substituent.

When R ₅₁ represents an alkoxy group, the alkyl part thereof represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. It may be substituted with a halogen atom, an aryl group, an alkoxy group or the like.

When R ₅₁ , R _52, or R ₅₃ represents a heterocyclic group, the heterocyclic group may be a carbon atom of the carbonyl group of the acyl group in the alpha acylacetamide or an amide group of an acyl group in one of the carbon atoms forming the ring. Combines with the nitrogen atom. Examples of such heterocycles include thiophene, furan, pyran,
Examples are pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine and oxazine. These may further have a substituent on the ring.

In the general formula (Cp-3), R ₅₅ is a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (eg, methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.), alkenyl group. (Eg allyl group), cyclic alkyl group (eg cyclopentyl group, cyclohexyl group, norbornyl group), aralkyl group (eg benzyl, β-phenylethyl group etc.), cyclic alkenyl group (eg cyclopentenyl, cyclohexenyl group etc.) Represents a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an arboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, Carbamoyl group, acylami Group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamine group, anilino group, N
-Arylanilino group, N-alkylanilino group, N-
It may be substituted with an acylanilino group, a hydroxyl group, a mercapto group or the like.

Further, R ₅₅ may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have one or more substituents, and examples of the substituent include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group and an alkoxy group. , Aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxy arbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl Group, alkylsulfonyl group,
Arylthio group, alkylthio group, alkylamino group,
It may have a dialkylamino group, an anilino group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino group, a hydroxyl group, and the like.

Further, R ₅₅ is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, a condensed heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group. , An oxazolyl group, an imidazolyl group, a naphthoxazolyl group, etc.), a heterocyclic group substituted by the substituents listed above for the aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group. Base,
It may represent an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

In the formula, R ₅₄ is a hydrogen atom and has 1 to 32 carbon atoms, preferably 1
To 32, preferably 1 to 22, straight chain or branched chain alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (these groups may have the substituents enumerated for R ₅₅ ) and aryl groups. And a heterocyclic group (these may have the substituents enumerated above for R ₅₅ ), an alkoxycarbonyl group (eg, a methoxycarbonyl group, an ethoxycarbonyl group, a stearyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, a phenyl group). Enoxycarbonyl group, naphthoxycarbonyl group etc.), aralkyloxycarbonyl group (eg benzyloxycarbonyl group etc.), alkoxy group (eg methoxy group, ethoxy group, heptadecyloxy group etc.), aryloxy group (eg phenoxy group, etc. Tolyloxy group, etc.), alkylthio group For example, ethylthio group, dodecylthio group etc.), arylthio group (eg phenylthio group, α-naphthylthio group etc.), carboxy group, acylamino group (eg acetylamino group, 3-[(2,4-di-tert-amylphenoxy) acetamide] Benzamide group), diacylamino group, N-alkylacylamino group (for example, N-methylpropionamide group), N
-Arylacylamino group (for example, N-phenylacetamido group), ureido group (for example, ureido, N-arylureido, N-alkylureido group, etc.), urethane group, thiourethane group, arylamino group (for example, phenylamino, N -Methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-5-tetradecanamidoanilino group, etc.), alkylamino group (for example, n-butylamino group, methylamino group, cyclohexylamino group, etc.), cyclo Amino group (eg piperidino group, pyrrolidino group etc.), heterocyclic amino group (eg 4-pyridylamino group, 2-benzoxazolylamino group etc.), alkylcarbonyl group (eg methylcarbonyl group etc.), arylcarbonyl group (eg Phenylcarbonyl group, etc. , A sulfonamido group (e.g., an alkylsulfonamido group, an aryl sulfonamide group), a carbamoyl group (e.g., an ethylcarbamoyl group,
Dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (for example, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N An -alkyl-N-arylsulfamoyl group,
N, N-diaryl sulfamoyl group, etc.), cyano group,
Represents either a hydroxy group or a sulfo group.

In the formula, R ₅₆ represents a hydrogen atom or a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, and these are It may have the substituents exemplified above for R ₅₅ .

Further, R ₅₆ may represent an aryl group or a heteroenvironmental group, and these may have the substituents enumerated above for R ₅₅ .

Further, R ₅₆ is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group,
Sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group , N
-Arylanilino group, N-alkylanilino group, N-
It may represent an acylanilino group or a hydroxyl group.

R ₅₇ , R ₅₈ and R ₅₉ each represent a group used in a usual 4-equivalent phenol or α-naphthol coupler, and specifically, R ₅₇ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group or an aliphatic carbon group. Hydrogen residue, N-arylureido group, acylamino group, -O-
R ₆₂ or -S-R ₆₂ (wherein R ₆₂ is an aliphatic hydrocarbon residue)
When two or more R _57's are present in the same molecule, the two or more R _57's may be different groups, and the aliphatic hydrocarbon residue has a substituent. including.

Further, when these substituents include an aryl group, the aryl group may have the substituents enumerated above for R ₅₅ .

Examples of R ₅₈ and R ₅₉ include an aliphatic hydrocarbon residue, a group selected from an aryl group and a heterocyclic residue, or one of these may be a hydrogen atom,
Also, those having a substituent in these groups are included. Also
R ₅₈ and R ₅₉ may together form a nitrogen-containing heterocyclic nucleus.

The hydrocarbon aliphatic residue may be saturated or unsaturated, and may be linear or branched.
Any of the annular ones may be used. And preferably an alkyl group (for example, each group of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.),
It is an alkenyl group (for example, each group such as allyl and octenyl). Typical examples of the aryl group include a phenyl group and a naphthyl group, and typical examples of the heterocyclic residue include pyridinyl, quinolyl, thienyl, piperidyl, and imidazolyl groups. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl,
Examples thereof include heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl and morpholino groups.

l represents an integer of 1 to 4, m represents an integer of 1 to 3, and p represents an integer of 1 to 5.

R ₆₀ is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and 1 to 32 carbon atoms, preferably 2 ~ 22 represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, and examples of the substituent include an alkoxy group, an alkoxycarbonyl group, an acylamino group,
Examples thereof include an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group or an aryl group.

R ₆₁ is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group,
Alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, alkoxycarbonyl group or aryloxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, alkyl having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms A sulfonyl group,
Arylsulfonyl group, aryl group, 5-membered or 6-membered heterocyclic group (as a hetero atom, selected from nitrogen atom, oxygen atom, and sulfur atom, for example, triazolyl group, imidazolyl group, phthalimido group, succinimido group, furyl group, pyridyl group A group or a benzotriazolyl group), which may have the substituent described in the above R ₆₀ .

Among the above coupler residues, as the yellow coupler residue, in the general formula (Cp-1), R ₅₁ is a t-butyl group or a substituted or unsubstituted aryl group, and R ₅₂ is a substituted or unsubstituted aryl group. Is preferred, and in the general formula (Cp-2), R ₅₂ and R ₅₃ are preferably a substituted or unsubstituted aryl group.

Preferred as the magenta coupler residue are those represented by the general formula (Cp
When R ₅₄ in -3) represents an acylamino group, a ureido group, and an arylamino group, and R ₅₅ represents a substituted aryl group, R ₅₄ in the general formula (Cp-4) represents an acylamino group, a ureido group, and an arylamino group, When R ₅₆ represents a hydrogen atom, and in the general formulas (Cp-5) and (Cp-6), R ₅₄ and R ₅₆ are linear or branched alkyl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, This is the case where it represents a cyclic alkenyl group.

Preferred as the cyan coupler residue is a compound represented by the general formula (Cp-
R ₅₇ in 7) is an acylamino group or ureido group at the 2-position, an acylamino group or an alkyl group at the 5-position,
When the 6-position represents a hydrogen atom or a chlorine atom, R ₅₇ in the general formula (Cp-9) is a 5-position hydrogen atom, an acylamino group, a sulfonamide group or an alkoxycarbonyl group, and R ₅₈ is a hydrogen atom. Further, R ₅₉ represents a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, and a cyclic alkenyl group.

Preferred as the uncolored coupler residue are those represented by the general formula (Cp-1
When R ₅₇ represents an acylamino group, a sulfonamide group or a sulfamoyl group in (0), the general formula (Cp-11)
In the case where R ₆₀ and R ₆₁ represent an alkoxycarbonyl group.

Further, at any part of R _{51 to} R ₆₁ , a bis or higher multimer may be formed, and a polymer or non-polymer of Monmer having an ethylenically unsaturated group at any part of these groups. It may be a copolymer with a color forming monomer.

When the coupler residue of the present invention represents a polymer, a polymer derived from a monomer coupler represented by the following general formula (Cp-12) and having a repeating unit represented by the general formula (Cp-13), Alternatively, it means a copolymer with an oxidant of an aromatic primary amine developing agent and at least one non-color-forming monomer containing at least one ethylene group which has no ability to couple. Here, two or more monomer couplers may be polymerized at the same time.

General formula (Cp-12) General formula (Cp-13) In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, A ₁ represents -CONR'-, -NR'CONR'-, -NR'COO-, -COO-,
_{-SO 2 -, - CO -,} - NR'CO -, - SO 2 NR '-, - NR'SO
_{2 -, - OCO -, -} OCONR '-, - NR'- or represents -O-, A ₂ represents -CONR'- or -COO-, R' is a hydrogen atom, an aliphatic group or an aryl group, When there are two or more R's in one molecule, they may be the same or different. A ₃ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group, and the alkylene group may be linear or branched. (Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and arylene groups such as phenylene,
Naphthylene, etc.) Q is any of R _{1 to} R _{11 in} the general formulas (Cp-1) to (Cp-11), and is a group bonded to the general formula (Cp-12) or (Cp-13). Represent.

i, j and k represent 0 or 1.

Here, the substituent of the alkylene group, aralkylene group or arylene group represented by A ₃ is an aryl group (for example, a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (for example, a methoxy group), an aryloxy group. (Eg phenoxy group), acyloxy group (eg acetoxy group), acylamino group (eg acetylamino group), sulfonamide group (eg methanesulfonamide group), sulfamoyl group (eg methylsulfamoyl group), halogen atom (eg fluorine group) Element, chlorine, bromine, etc.), a carboxy group, a carbamoyl group (eg, methylcarbamoyl group), an alkoxycarbonyl group (eg, methoxycarbonyl group, etc.), and a sulfonyl group (eg, methylsulfonyl group). When there are two or more of these substituents, they may be the same or different. Next, as the non-color-forming ethylenic monomer that does not couple with the oxidation product of the aromatic primary amine developing agent, acrylic acid or α-chloroacrylic acid is used. , Α-alkyl acrylic acid (for example, ester or amide derived from acrylic acids such as acrylic acid and methacrylic acid (for example, acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, n-propyl acrylate) , Iso−
Propyl acrylate, n-butyl acrylate, t-
Butyl acrylate, n-butyl methacrylate, 2-
Ethylhexyl acrylate, n-hexyl acrylate, n-octyl acrylate, lauryl acrylate, and methylenebisacrylamide), vinyl esters (for example, vinyl acetate, vinyl propionate, and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds ( For example styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene),
Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid ester, N-vinyl-2-
Pyrrolidone, N-vinyl pyridine, and 2- and 4
-Vinyl pyridine and the like. Especially acrylic acid ester,
Methacrylic acid ester and maleic acid ester are preferable. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can be used together. For example, n-
Butyl acrylate and divinylbenzene, styrene and methacrylic acid, n-butyl acrylate and methacrylic acid, etc. can be used.

The compound (a) which is oxidized to form a development inhibitor or a precursor thereof according to the present invention is formed by a reaction with an oxidized product of a developing agent, or (b) the compound which is oxidized to form a development inhibitor or a precursor thereof. Specific examples of the compound produced by the reaction of the precursor of (1) with the oxidized product of the developing agent are shown below, but the invention is not limited thereto.

The compound represented by formula (I) of the present invention is disclosed in
-33059, 59-136973, US Patent 4,248,962, UK Patent (Publication) 2,072,363, and Patent Application (B) on April 5, 1985, Patent Application (C) on April 5, 1985, April 8 Date of patent application (A), April 12 of the same year Date of patent application (B), April of the same year
It can be synthesized by the method described in the specification attached to each application of Japanese Patent Application No. 15 (A) [15] dated (Fuji Photo Film Co., Ltd.).

The reason why the compound of the present invention exhibits good performance with the added amount of the present invention is not clear, but it can be considered as follows.

Japanese Patent Application No. 59-33059 discloses compounds represented by the following general formula.

General formula A-RED-PUG (In the formula, A is coupled to the oxidation product of the developing agent by a coupling reaction to RE
Represents a coupler residue that releases D-PUG, and RED binds to A.
After cleavage, after redox reaction with oxidized form of developing agent
Represents a group that releases PUG, and PUG cleaves its bond with RED.
Represents a group which substantially exhibits a photographic effect after ) This compound is released by reaction with oxidized developing agent.
RED-PUG (PUG represents a development inhibitor in the present invention)
Becomes OX-PUG due to another molecule of oxidized developing agent.
For the first time, PUG can be released (where OX is R
Represents the oxidant of ED). In addition, the hydroxylation in the developer
Product ion (OH ), Sulfite ion, hydroxylamine
It releases PUG in response to a nucleophilic attack such as. Therefore,
Process of first-stage redox reaction (RED-PUG → OX-PUG)
Compared with conventional DIR compounds, it produces oxidized developer
Large amount of silver in silver halide determines rate and amount produced
Sulfite will depend heavily on and determines the release rate
Ions, hydroxide ions, hydroxylamine, etc.
It also reacts with this developing agent oxidant and is consumed.
Therefore, the second step of the nucleophilic reaction (OX-PUG + Nu → OX-Nu + P
UG, where Nu means a nucleophile), and
It seems that it will depend heavily on it. Therefore, the present invention
In a silver halide emulsion layer containing a compound of
The amount of the compound of the present invention relative to silver is within the above range.
It is estimated that significant improvements in photographic performance can be achieved.
It

The multilayer color photographic material of the present invention has at least one red-sensitive emulsion layer, green-sensitive emulsion layer, and blue-sensitive emulsion layer on the support. The order of these layers can be arbitrarily selected as required. It is usual to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases.

The same or other photographic emulsion layers or non-light-sensitive layers of the photographic light-sensitive material prepared by using the present invention can have the above-mentioned general formula (I).
And a compound represented by a color coupler, that is, an aromatic primary amine developing agent (eg,
A compound capable of forming a color by oxidative coupling with a phenylenediamine derivative or an aminophenol derivative) may be used.

Useful color couplers are cyan, magenta and yellow color couplers, typical examples of which are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure 1
7643 (December 1978) VII-D and 18717 (November 1979)
Monthly).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent color coupler in which the coupling active position is replaced by a leaving group is more preferable than a four-equivalent color coupler in which a hydrogen atom is present, because the coated silver group can be reduced and high sensitivity can be obtained. A coupler in which the color-forming dye has an appropriate diffusibility, a colorless coupler or a coupler which releases a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. Two equivalent yellow couplers include U.S. Pat.Nos. 3,408,194, 3,447,928, and 3,993,501.
Nos. 4,022,620 and the like, or oxygen atom-releasing yellow couplers or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, and RD18053 (197).
April 9), British Patent No. 1,425,020, West German Application Publication No. 2,
Representative examples thereof include nitrogen atom-releasing yellow couplers described in No. 219,917, No. 2,261,361, No. 2,329,587 and No. 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of magenta couplers that can be used in combination with the present invention include oil-protection type isazozolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230.
(June 1984), and pyrazolopyrazoles. The imidazo compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers that can be used in combination with the present invention include oil-protective naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of phenol-based couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or higher at the meta position of the phenol nucleus described in US Pat. No. 3,772,002. Cyan coupler, U.S. Pat.
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 58-42671, 2,5-diacylamino-substituted phenol couplers and U.S. Patents Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
No. 7,767, and the like, phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like.

In order to correct the unnecessary absorption in the short wavelength region which the dyes formed from the magenta and cyan couplers have, it is preferable to use a colored coupler together with the color photosensitive material for photographing. Yellow colored magenta couplers described in U.S. Pat.No. 4,163,670 and JP-B-57-39413 or U.S. Pat.Nos. 4,004,929, 4,138,258 and British Patent 1,
Typical examples are magenta colored cyan couplers described in JP-A No. 146,368 and the like.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Specific examples of magenta couplers are described in U.S. Pat. No. 4,366,237 and British Patent 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

These couplers may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, it may be a colored coupler having an effect of color correction.

In addition to the DIR coupler, a non-color-forming DIR coupling compound which has a colorless coupling-reactive product and releases a development inhibitor may be contained. In addition to the DIRA coupler, the photosensitive material may contain a compound which releases a development inhibitor upon development.

The above-mentioned various couplers may be used in combination of two or more kinds in the same photographic layer in order to satisfy the properties required for the light-sensitive material, or the same compound may be introduced in two or more different layers. You can also

A known method for introducing the coupler of the present invention and the coupler which can be used together in a silver halide emulsion layer is known, for example, in US Pat.
The method described in No. 2,322,027 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, dioctyl butyl phosphonate), citric acid ester (eg acetyl) Tributyl citrate), benzoic acid ester (eg octyl benzoate), alkylamide (eg diethyl laurylamide), fatty acid ester (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid ester (eg tributyl trimesate) , Or an organic solvent having a boiling point of 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxy After being dissolved in ethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, the dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be either lime-treated or acid-treated. See Arthur Weiss for details on how to make gelatin.
Author, The Macromolecular Chemistry of Gelatin,
(Academic Press, 1964).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide containing 15 mol% or less of silver iodide.
Particularly preferred is silver iodobromide containing 2 to 12 mol% of silver iodide.

The average grain size of the silver halide grains in the photographic emulsion (the grain diameter in the case of spherical grains or grains close to spheres, the edge length in the case of cubic grains, and the average based on the projected area) is particularly required. However, it is preferably 3 μm or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubes and octahedra, and spherical,
Those having an irregular crystal body such as a plate shape, or a composite form of these crystal forms may be used. It may consist of a mixture of particles of different crystal forms.

It is also possible to use an emulsion in which ultra-thin tabular silver halide grains having a grain diameter 5 times or more the thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and outside. Further, it may be a particle in which a latent image is mainly formed on the surface or a particle in which a latent image is mainly formed inside the particle.

The photographic emulsion used in the present invention is P. glackid (P.
Glafkides), "Chimie et Physique Photographique"
(Published by Paul Montel, 1966),
VLZelikman, et al.,
"Making and Coating Photographi
c Emulsion ”(published by The Focal Press, 1964) and the like. That is, any of the acid method, neutral method, ammonia method, etc. The soluble silver salt and the soluble halogen salt may be reacted with each other by a one-sided mixing method, a simultaneous mixing method, a combination thereof, or the like.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as one type of simultaneous mixing method.
Can also be used, that is, a so-called controlled double jet method can be used.

According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt and the like may coexist.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, Etch Freezer (H.Friese
r) ed., "Die Grundlagender Photographischen Pro".
zesse mit Silber Halogeniden) ”(Academic
Fuel Larks Gezershyaft (Akademische Verlagsg
esellschaft), 1968), pp. 675-734.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, first tin salt, Reduction sensitization of amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds; precious metal compounds (eg gold complex salts, Pt, Ir,
A noble metal sensitizing method using a periodic salt group VIII metal complex salt such as Pd) or the like can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc .; Emissions Zen thiosulfate Huong acid, benzenesulfonic fins acid, known as antifoggants or stabilizers such as benzene Huong acid amide, can be added a number of compounds.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in smoothness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary anomium salt. Compound, urethane derivative,
It may contain a urea derivative, an imidazole derivative, 3-pyrazolidones and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination with them. Acrylic acid, methacrylic acid,
A polymer having a monomer component of a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, and styrene sulfonic acid can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, odanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone. A combination thereof may be used, and a combination of sensitizing dyes is often used particularly for the purpose of supersensitization.

A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Aminostil compounds substituted with nitrogen-containing heterocyclic groups (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,743,510), cadmium salts ,
An azaindene compound or the like may be included.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chromium deuterium, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane) Etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.), and the like can be used alone or in combination.

In the light-sensitive material produced by using the present invention, when the hydrophilic colloid layer contains a dye or an ultraviolet absorber, they may be mordanted with a cationic polymer or the like.

The light-sensitive material produced by using the present invention may contain, as a color antifoggant, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative and the like.

The light-sensitive material produced by using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (for example, JP-A- 46-278
4), cinnamic acid ester compounds (for example, those described in US Pat. Nos. 3,705,805 and 3,707,375),
A butadiene compound (for example, one described in US Pat. No. 4,045,229) or a benzoxazole compound (for example, one described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in a specific layer.A light-sensitive material produced by using the present invention contains a water-soluble dye as a filter dye in a hydrophilic colloid layer or for various purposes such as prevention of irradiation. It may be contained. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more kinds. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

Photographic processing of layers consisting of photographic emulsions made using the present invention include, for example, Research Disclosure 176, Nos. 28-3.
Any known method and known processing solution as described on page 0 can be applied. The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfoamidoethylaniline, 4-amino-3-
Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

In addition, FA Mason, “Photographic Processing Chemistry (Phot
ographic Processing Chemistry) ”(Foca Press
Press), 1966), pp. 226-229, U.S. Pat.
Those described in 93,015, 2,592,364 and JP-A-48-64933 may be used.

Color developers also include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides,
A development inhibitor such as iodide and an organic antifoggant or an antifoggant can be contained. If necessary, a water softener, a preservative such as hydroxylamine,
Organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid chelating agents, antioxidants It may also contain agents.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used.

For example, ferricyanide, dichromate, iron (III)
Or an organic complex salt of cobalt (III) such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2
-Aminopolycarboxylic acids such as propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates; nitrosphenol and the like can be used. Of these, potassium ferrocyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

As the fixer, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Here, after the fixing step or the bleach-fixing step, washing with water,
Although it is common practice to carry out a treatment step such as stabilization, only a water washing step is carried out, and conversely, a substantial water washing step is not provided and only a stabilizing treatment step is carried out (Japanese Patent Laid-Open No. 57-8).
A simple treatment method such as Japanese Patent No. 543) can also be used.

The washing water used in the washing step may contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, bactericides / antifungal agents that prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, drying load, unevenness It is possible to use a surfactant or the like for preventing the above. Or LE West
st), “Water Quality Criteria (Wate
r Quality Criteria) ”Photographic Science and Engineering (Phot.Sci.and En
g.), Vol. 9 No. 6 Page 344 to 359 (1965) and the like can also be used.

In addition, the washing step may be performed using two or more tanks if necessary, and the washing water may be saved as multi-step countercurrent washing (for example, 2 to 9 steps).

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), and the like can be used. If necessary, a fluorescent whitening agent, a chelating agent, a bactericidal agent, an antifungal agent, a hardener, a surfactant and the like can be used in the stabilizing solution.

In addition, the stabilizing step may be performed using two or more tanks if necessary, and multi-stage countercurrent stabilization (for example, 2 to 9 steps) is performed to save the stabilizing solution, and the washing step may be omitted. You can also

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A multi-layer color light-sensitive material (101) having the following composition was formed on a transparent triacetyl cellulose film support.

1st layer: anti-halation layer Black colloidal silver …… 0.15g / m ² UV absorber U-1 …… 0.08g / m ² U-2 …… 0.12g / m ² Oil 1 …… 0.10g / m ² Gelatin: 1.2 g / m ² Second layer: Intermediate layer 2,5-di-t-pentadecylhydroquinone: 0.18 g / m ² Coupler C-1: 0.11 g / m ² Gelatin: 1.1 g / m ² Third layer: First red-sensitive emulsion layer Silver iodobromide …… 1.2g / m ² Sensitizing dye I …… 1.4 × 10 ^-4 moles to 1 mole of silver Ⅱ II …… 0.4 × 10 ^-4 moles to 1 mole of silver Ⅲ ……… to 1 mole of silver 5.6 × 10 ^-4 moles Same IV …… 4.0 × 10 ^-4 moles per silver mole Coupler C-2 …… 0.051 moles per silver mole Coupler C-3 …… 0.0040 per mole silver Molar coupler C-4 ... 0.0040 mol per mol of silver Oil 2 ... 0.35 g / m ² Gelatin ... 1.7 g / m ² 4th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion …… 1.0g / m ² Sensitizing dye I …… 5.2 × 10 ^-5 moles to 1 mole of silver II ………… 1.5 × 10 ^-5 moles to 1 mole of silver III …… to 1 mole of silver 2.1 × 10 ^-4 mol Same IV …… 1.5 × 10 ^-5 mol for 1 mol silver Coupler C-2 …… 0.0068 mol for 1 mol silver Coupler C-5 …… 0.012 for 1 mol silver Molar coupler C-3: 0.0048 mol of oil per mol of silver 2: 0.20 g / m ² gelatin: 1.2 g / m ² 5th layer; intermediate layer: 2,5-di-t-pentadecylhydroquinone … 0.08 g / m ² gelatin …… 0.9 g / m ² 6th layer; 1st green-sensitive emulsion layer Silver iodobromide …… 0.60g / m ² Sensitizing dye V …… 4.0 × 10 ^-4 moles to 1 mole silver Same VI …… 3.0 × 10 ^-5 moles to 1 mole silver VII …… To 1 mole silver 1.0 × 10 ^-4 mol Coupler C-6 …… 0.077 mol for 1 mol silver Coupler C-7 …… 0.022 mol for 1 mol silver Coupler C-8 …… 0.0035 mol for 1 mol silver Compound (4) of the invention: 0.002 mol of oil per mol of silver 1: 0.35 g / m ² Gelatin: 1.0 g / m ² 7th layer: 2nd green emulsion layer Silver iodobromide …… 1.00 g / m ² Sensitizing dye V …… 2.7 × 10 ^-4 moles to 1 mole of silver VI VI …… 1.8 × 10 ^-5 moles to 1 mole of silver VII ………… to 1 mole of silver 7.5 × 10 ^-5 moles Coupler C-6 …… 0.013 moles per 1 mole silver Coupler C-7 …… 0.0020 moles per 1 mole silver Oil 1 …… 0.26 g / m ² Gelatin …… 0.90 g / m ² Eighth layer: Yellow filter layer Yellow colloidal silver …… 0.08g / m ² 2,5-di-t-pentadecylhydroquinone …… 0.090g / m ² Oil 1 …… 0.35g / m ² Gelatin …… 1.3 g / m ² 9th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion …… 0.37g / m ² Sensitizing dye VIII …… 4.4 × 10 ^-4 moles coupler to 1 mole silver C-9 …… 0.26 moles coupler to 1 mole silver C-4 …… to 1 mole silver Te 0.015 mol oil 1 ...... 0.28g / m ² gelatin ...... 1.0 g / m ² 10th layer: second blue-sensitive emulsion layer silver iodobromide emulsion …… 0.55g / m ² Sensitizing dye VIII …… 3.0 × 10 ^-4 mol for 1 mol of silver Coupler C-9 …… 0.057 mol for 1 mol of silver Oil 1 …… 0.10 g / m ² Gelatin …… … 0.60g / m ² 11th layer; 1st protective layer UV absorber U-1… 0.14g / m ² same U-2… 0.22g / m ² oil 1 …… 0.025g / m ² oil 2 …… 0.015 g / m ² gelatin ...... 0.78g / m ² 12th layer: second protective layer silver iodobromide emulsion …… 0.25 g / m ² polymethacrylate particles (diameter 1.5 μ) …… 0.10 g / m ² gelatin …… 1.0 g / m ² Each layer contains gelatin hardener H-1 and surfactant in addition to the above composition. Applied.

(Samples 102 to 115) Samples 102 to 115 are the same as Sample 101 except that the addition amount and species of the compound (4) of the present invention added to the sixth layer of Sample 101 are changed as shown in Table 1. Created 115.

Using the A light source for these samples, with a color temperature conversion filter
The temperature was adjusted to 4800 ° K, exposure was carried out at 20 CMS, and the following color development was carried out at 38 ° C.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each process is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-Nβ-hydroxyethylamino)-
2-Methylaniline sulfate 4.5g Water added 1.0l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0 l pH 6.0 Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added 1.0 l pH 6.6 Stabilizing solution Formalin (40%) 2.0 ml Polyoxy Ethylene-P-monononylphenyl ether (average degree of polymerization ≈10) 0.3g Water was added to 1.0l Also, exposure was performed through a pattern for MTF measurement, and the above color development processing was performed. The MTF value in 40 cycles was measured.

The results obtained are summarized in Table 1.

It can be seen from Table 1 that the compounds of the present invention have too large a development inhibiting effect at a certain addition amount or more, so that the sensitivity is remarkably lowered. Further, it can be seen that the sample to which the addition amount of the present invention is applied has a large CTF value and is excellent in sharpness as compared with the conventional sample in which the sensitivity is almost the same by adding the DIR coupler.

Example 2 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material 201 was prepared by applying each layer having the following composition in multiple layers.

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

1st layer: anti-halation layer Black colloidal silver ...... Silver 0.18 gelatin ...... 1.28 2nd layer; Intermediate layer 2,5-di-t-pentadecyl hydroquinone ...... 0.18 C-1 ...... 0.12 Oil 1 (solvent) ... … 0.17 Oil 2 (same as above) …… 0.02 Gelatin …… 1.04 3rd layer; 1st red emulsion layer Silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.8μ)… Silver 1.71 Sensitizing dye IX …… 6.9 × 10 ^-5 Sensitizing dye II …… 1.8 × 10 ^-5 Sensitizing dye III …… 3.1 × 10 ^-4 Sensitizing dye IV …… 4.0 × 10 ^-5 C-2 …… 0.063 C-3… … 0.0005 C-12 …… 0.0032 Oil 1 (coupler 2,3 solvent) ・ ・ ・ 0.31 Gelatin ・ ・ ・ 1.84 4th layer; 2nd red emulsion layer Silver iodobromide emulsion (5 mol% silver iodide, average grain size) 0.85Myu) increase ...... silver 1.15 sensitizing dye IX ...... 5.1 × 10 ^-5 sensitizing dye II ...... 1.4 × 10 ^-5 sensitizing dye III ...... 2.3 × 10 ^-4 sensitizing dye IV ...... 3.0 × 10 ^{- 5} C-2 ...... 0.052 C-3 ...... 0.002 C-5 ...... 0.01 0 Oil 1 (coupler solvent) ...... 0.25 Oil 3 (same as above) ...... 0.07 Gelatin ...... 1.69 Fifth layer; third red emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.5μ ) ……
Silver 1.89 Sensitizing dye IX ...... 5.4 × 10 ^-5 Sensitizing dye II …… 1.4 × 10 ^-5 Sensitizing dye III …… 2.4 × 10 ^-4 Sensitizing dye IV …… 3.1 × 10 ^-5 C-5… … 0.014 C-3 …… 0.003 Oil 1 (Coupler solvent) …… 0.32 Gelatin …… 1.63 6th layer; Intermediate layer Gelatin …… 1.06 7th layer; 1st green sensitive emulsion layer Silver iodobromide emulsion (silver iodide) 6 mol%, average particle size 0.8 μ) Silver 0.58 Sensitizing dye V …… 3.0 × 10 ^-5 Sensitizing dye VI …… 1.0 × 10 ^-4 Sensitizing dye VII …… 3.8 × 10 ^-4 C-13 …… 0.071 C-1 …… 0.007 C-7 …… 0.010 C-4 …… 0.006 Oil 1 (coupler solvent) …… 0.14 Gelatin …… 0.70 8th layer; 2nd green emulsion layer Silver iodobromide emulsion ( 5 mol% silver iodide, average grain size 0.85μ)
Silver 1.65 Sensitizing dye V …… 2.1 × 10 ^-5 Sensitizing dye VI …… 7.0 × 10 ^-5 Sensitizing dye VII …… 2.6 × 10 ^-4 C-14 …… 0.021 C-13 …… 0.006 C-1 …… 0.001 C-7 …… 0.0006 C-4 …… 0.001 Oil 1 (coupler solvent) ・ ・ ・ 0.45 Oil 2 ・ ・ ・ 0.08 Gelatin ・ ・ ・ 1.97 9th layer; 3rd green sensitive emulsion layer Silver iodobromide emulsion (iodine Silver halide 10 mol%, average particle size 1.5μ) Silver 2.27 Sensitizing dye V …… 3.5 × 10 ^-5 Sensitizing dye VI …… 8.0 × 10 ^-5 Sensitizing dye VII …… 3.0 × 10 ^-4 C -15 …… 0.009 C-1 …… 0.001 Oil 1 (coupler solvent) …… 0.69 Oil 2 (same as above) …… Gelatin …… 2.39 10th layer; Yellow filter layer Yellow colloidal silver …… Silver 0.05 2,5-di -T-pentadecylhydroquinone ...... 0.03 gelatin ...... 0.95 11th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6 µ) ......
Silver 0.24 C-9 ...... 0.27 C-4 ...... 0.005 Oil 1 (coupler solvent) ...... 0.28 Gelatin ...... 1.28 12th layer; 2nd blue sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, Average particle size 1.0 μ) ...... Silver 0.45 Sensitizing dye VIII ...... 2.1 × 10 ^-4 C-9 ...... 0.098 Compound of the present invention (6) ...... 0.015 Oil 1 (coupler solvent) ...... 0.03 Gelatin ...... 0.46 13th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (10 mol% silver iodide, average grain size 1.8μ) ...... Silver 0.77 Sensitizing dye VIII ...... 2.2 × 10 ^-4 C-9 ...... 0.036 Oil 1 (Coupler solvent) ...... 0.07 Gelatin ...... 0.69 14th layer; 1st protective layer Silver iodobromide (silver iodide 1 mol%, average particle size 0.07μ) ...... Silver 0.5 UV-1 ...... 0.11 UV -2 ...... 0.17 Oil 3 (UV-1,2 solvent) ...... 0.90 15th layer; 2nd protective layer Polymethylmethacrylate particles (diameter 1.5 μm) ...... 0.54 Gelatin ...... 0.72 The above composition for each layer Others Keratin was added hardener H-1 and surfactants.

Oil 1 shown in the above composition is tricresyl phosphate, oil 2 is dibutyl phthalate, and oil 3 is trihexyl phosphate. The chemical composition of other components is shown later.

(Samples 202 to 208) Sample 202 was prepared in the same manner as Sample 201 except that the addition amount and species of the compound (6) of the present invention added to the 12th layer of Sample 201 were changed as shown in Table 2. Created ~ 208.

48 samples with a color temperature conversion filter using light source A
The photographic performance was evaluated by adjusting the temperature to 00 ° K, applying the exposure of 5 CMS, and performing the same processing as in Example 1. The same color development was performed by exposing through the same MTF measurement pattern, and the MTF value at 40 cycles per 1 mm of the yellow image was measured.

From Table 2, it can be seen that the sample using the compound of the present invention in the addition amount of the present invention has high sensitivity and good sharpness represented by MTF value.

Structure of compounds used in Examples 1 and 2 _{H-1 CH 2 = CH-} SO 2 -CH 2 -CONH (CH 2) 2 NHCO-CH 2 -SO 2 -CH = C
H ₂ Sensitizing dye

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
In a silver halide color photographic light-sensitive material having a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, at least one light-sensitive layer is composed of two or more layers having different sensitivities, and the highest sensitivity layer among them. (A) A compound which forms a development inhibitor or its precursor only after being oxidized in a silver halide emulsion layer other than those produced by a reaction with an oxidized product of a developing agent, or (b) a development inhibitor or a compound which forms a precursor thereof only after being oxidized. A compound represented by the following general formula (I), which is formed by reacting a precursor of a compound which forms the precursor with an oxidized product of a developing agent, is added to the silver halide in the photosensitive layer at most 5 parts.
A silver halide color photographic light-sensitive material characterized by containing mol%. In formula (I) A-B-D, A represents a coupler residue that cleaves the bond between A and B upon reaction with an oxidized product of a developing agent, and B is oxidized after the bond between A and C is cleaved. Represents a group that cleaves the bond between B and D or a precursor thereof, and D represents a development inhibitor or a precursor thereof.