JPH10288830A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide color photographic sensitive material small in drop of a cyan color image density even in the case of using a fatigued bleaching solution or bleach fixing solution by incorporating a specified cyan dye-forming coupler and further a specified compound. SOLUTION: This color photosensitive material contains the cyan dye-forming coupler represented by formula I and one of the compounds represented by formulae II and III. In formulae I-III, R1 is an optionally substituted aromatic or aliphatic group or the like; X is an H atom or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent; R2 is not an H atom but a group substitutable on a benzene ring; (n) is an integer of 1-5; each of R6 -R9 is, independently, an H atom or an aliphatic group or the like; Y is an H atom or an optionally substituted aliphatic group or the like; and Z is a nonmetallic atomic group necessary to form a 5- or 6-membered ring together with another groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a fatigue bleaching solution or a fatigue bleach-fixing solution having high sensitivity, high color development, excellent color image fastness and weak oxidizing power. The present invention relates to a silver halide color photographic light-sensitive material excellent in processing stability, in which a decrease in the density of a cyan dye image is small even when processed. Further, the present invention relates to a silver halide color photographic light-sensitive material in which a decrease in the density of a cyan dye image is small even after rapid processing.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is subjected to a color development treatment after exposure, whereby an oxidized paraphenylenediamine-based color developing agent reacts with a coupler to generate a dye, whereby a color image is formed. It is formed. Generally, in this method, a color reproduction method based on a subtractive color method is employed, and a yellow, magenta, and cyan color image is formed.

As a cyan dye-forming coupler (cyan coupler), phenols and naphthols are representative. Among them, naphthols have been widely used for color negative films because they can have a sufficiently long wave and have high coupling activity.

However, phenol couplers and naphthol couplers, which have been widely used, are weak in oxidizing power due to fatigue of the bleaching or bleach-fixing solution during processing.
There is a disadvantage that a sufficient color image density cannot be obtained. This phenomenon is caused by the fact that cyan dye is reduced to leuco dye by ferrous ions generated by bleaching the developed silver in the bleaching or bleach-fixing process, and is not reoxidized to dye due to fatigue of the solution (recovery). Poor color).

[0005] Various studies have hitherto been made to improve such disadvantages. For example, JP-A-56-6513
No. 4, No. 57-204543, etc., phenolic cyan couplers having a phenylureido group at the 2-position and a carboxamide group at the 5-position have been developed. Although the color reversal failure is improved, the coupling activity of the coupler is not always high, so that it was insufficient for use as a high-sensitivity color negative film photosensitive material.

Also, US Pat. No. 3,488,193,
The 2-arylcarbamoyl-substituted, 1-naphthol couplers described in JP-A-62-83747 and the like have high coupling activity and improved poor recoloring, but they can be said to have sufficient recoloring properties. Did not.

Further, cyan images formed from these phenol-based or naphthol-based couplers are not sufficient from the viewpoint of image fastness.

On the other hand, a 1-naphthol coupler having a specific substituent at the 5-position described in JP-A-61-153640 and the like has satisfactory performance in both coupling activity and dichroism. As described in JP-A No. 62-121457, there is a problem that a photosensitive material containing the coupler is stained when exposed to light for a long time after development processing. This problem can be solved by using the additives described in the patent together, but at the same time, the coloring property is reduced, and the patent does not disclose any solution.

In recent years, there has been an increasing demand for rapid development processing. However, a bleaching solution or a bleach-fixing solution for rapid processing is required to increase p.
H tends to be set lower. When processing a photosensitive material containing a cyan coupler with a fatigue bleaching solution for the purpose of rapid processing, poor recoloring tends to occur due to the pH dependence of the dye reduction potential. He did not always respond to the problem.

[0010]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a silver halide color photographic light-sensitive material having a small decrease in cyan image density even when processed using a fatigued bleaching solution or bleach-fixing solution. Is to provide.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and high color-forming property and excellent color reproducibility.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in the fastness of a cyan image.

[0013]

The above objects of the present invention have been attained by the following constitutions.

(1) A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, comprising a cyan dye-forming coupler represented by the following general formula [I]: And [(at least one selected from compounds represented by the following general formula [II] and compounds represented by the general formula [III]) and (compounds represented by the following general formula [IV] and the general formula [IV] At least one member selected from the group consisting of compounds represented by the formula [V]).

[0015]

Embedded image

[In the formula, R ₁ represents a substituted or unsubstituted aromatic group, an aliphatic group, or a heterocyclic group, and X represents a hydrogen atom or a coupling with an oxidized aromatic primary amine developing agent. Represents a group which can be removed by a reaction. ]

[0017]

Embedded image

[In the formula, R ₂ represents a group which can be substituted on a benzene ring other than a hydrogen atom, and n represents an integer of 1 to 5. When n is 2 or more, R ₂ may be the same or different. ]

[0019]

Embedded image

[Wherein, R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic group, aromatic group or heterocyclic group. ]

[0021]

Embedded image

Wherein R ₆ , R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an aliphatic group or an aromatic group;
Represents a hydrogen atom, a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, aliphatic or aromatic acyl group, aliphatic or aromatic oxycarbonyl group, and Z is

[0023]

Embedded image

Represents a group of nonmetallic atoms necessary for forming a 5- to 6-membered ring together with the group. ]

[0025]

Embedded image

[Wherein R ₁₀ and R ₁₁ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic group,
Or a heterocyclic group, R ₁₂ represents a group that can be substituted on a benzene ring, and m represents an integer of 0 to 5. When m is 2 or more, R ₁₂ may be the same or different. (2) The silver halide color photographic material as described in (1), wherein in the general formula [I], R ₁ is represented by the following general formula [VI].

[0027]

Embedded image

[In the formula, R ₁₃ represents a halogen atom, a substituted or unsubstituted aliphatic oxy group or an aromatic oxy group, and R ₁₄ represents a substituted or unsubstituted aliphatic group, aromatic group, or aliphatic group. Represents an oxy group or an aromatic oxy group;
Represents an integer of 1 to 4. Hereinafter, the present invention will be described in detail.

First, the cyan dye-forming coupler represented by formula (I) will be described.

[0030]

Embedded image

[In the formula, R ₁ represents a substituted or unsubstituted aromatic group, aliphatic group or heterocyclic group, and X represents a hydrogen atom or a coupling-off group. As the aromatic group represented by R ₁ , a substituted or unsubstituted phenyl group or a naphthyl group is preferable, and has 6 to 30 carbon atoms.
Is particularly preferred. Preferred substituents for the aromatic group include an alkoxy group (eg, methoxy group, t-butyloxy group, methoxyethyloxy group, etc.), an alkyl group (eg, methyl group, t-octyl group, etc.), an oxycarbonyl group (eg, Methoxycarbonyl group, isopropyloxycarbonyl group, dodecyloxycarbonyl group, phenoxycarbonyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), ureido group (eg, methylureido group, phenylureido group, etc.), acyloxy Group (eg, acetyloxy group, benzoyloxy group, etc.), carbonamide group (eg, acetamido group, tetradecaneamide group, etc.), sulfonamide group (eg, hexadecylsulfonamide group, phenylsulfonamide group, etc.), carbamoyl group (For example,
Dodecylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, tetradecylsulfamoyl group, N, N-diethylsulfamoyl group, phenylsulfamoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, p- A toluenesulfonyl group, an alkylthio group (eg, a hexadecylthio group, etc.), an arylthio group (eg, a 2-methoxyphenylthio group, etc.),
Aryl group (eg, 4-t-octylphenyl group, etc.), aryloxy group (eg, 2,4-di-t-amylphenoxy group, etc.), nitro group, cyano group, halogen atom, heterocyclic group (eg, N-dodecylpiperazino group) and the like.

The aliphatic group represented by R ₁ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and may be any of linear, branched or cyclic. Examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, a pentyl group, a t-butyl group, a hexadecyl group, a cyclohexyl group, and the like. Preferred substituents for the aliphatic group include an aromatic oxy group (for example, 2,4-di-t-amylphenoxy group, 2-chlorophenoxy group, etc.), an aliphatic oxy group (for example, methoxy group,
Dodecyloxy group), oxycarbonyl group (eg, methoxycarbonyl group) and the like.

The heterocyclic group represented by R ₁ has 2 carbon atoms.
To 30 substituted or unsubstituted heterocyclic groups are preferred.

X represents a hydrogen atom or a coupling-off group. Examples of the coupling-off group include a halogen atom, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic thio group, an aromatic thio group, a heterocyclic thio group, a heterocyclic ring, and an aromatic azo group. Can be Preferred X is a hydrogen atom, a halogen atom, an aliphatic oxy group having 1 to 30 carbon atoms (for example, methoxy group, methyloxycarbonylmethoxy group, 2-methoxyethylcarbamoylmethoxy group, 2-methanesulfonylethoxy group, A carboxymethylthioethoxy group and the like; an aromatic oxy group having 6 to 30 carbon atoms (for example, a phenoxy group, a 4-acetamidophenoxy group, a 2-nitrophenoxy group and a 4-phenylazophenoxy group); A heterocyclic oxy group (eg, 1-phenyl-5-pyrazolyloxy group), an aliphatic thio group having 1 to 30 carbon atoms (eg, carboxyethylthio group), an aromatic thio group having 6 to 30 carbon atoms (eg, , 2,4-di-t-amylphenylthio group and the like, and a heterocyclic thio group having 2 to 30 carbon atoms (for example, 1
-Phenyltetrazol-5-ylthio group), a heterocyclic group having 1 to 30 carbon atoms and connected to the active position of the coupler by a nitrogen atom (for example, succinimide group, hydantoinyl group, pyrazolyl group, triazolyl group, 2- Benzotriazolyl group and the like; and aromatic azo groups having 6 to 30 carbon atoms (for example, phenylazo group and 4-methoxyphenylazo group and the like).

Next, the general formula [VI], which represents a preferable embodiment of R ₁ in the general formula [I], will be described.

[0036]

Embedded image

[In the formula, R ₁₃ represents a halogen atom, a substituted or unsubstituted aliphatic oxy group, or an aromatic oxy group, and R ₁₄ represents a substituted or unsubstituted aliphatic group, an aromatic group,
Represents an aliphatic oxy group or an aromatic oxy group, and k is 1
Represents an integer from to 4. As the aliphatic oxy group represented by R ₁₃ or R ₁₄ , a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, a butoxy group,
Examples include a t-butyloxy group, an octyloxy group, and a dodecyloxy group. Preferred substituents include an aliphatic oxy group (eg, methoxy group, dodecyloxy group, etc.), an aromatic oxy group (eg, 2,4-di-t-amylphenoxy group, 2-chlorophenoxy group, etc.), oxy Examples include a carbonyl group (for example, a methoxycarbonyl group) and a hydroxyl group.

The aromatic oxy group represented by R ₁₃ and R ₁₄ is preferably a substituted or unsubstituted phenoxy group having 6 to 30 carbon atoms. Preferred substituents include the same as the preferred substituents for the aromatic group represented by R ₁ in the formula [I].

The aliphatic group represented by R ₁₄ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and may be any of linear, branched or cyclic. Examples of the aliphatic group include a methyl group, an ethyl group, a propyl group,
t-butyl group, s-butyl group, t-octyl group, nonyl group, dodecyl group, hexadecyl group, cyclohexyl group,
And the like. Preferred substituents on the aliphatic group include an oxycarbonyl group (eg, methoxycarbonyl group, octyloxycarbonyl group, phenoxycarbonyl group, etc.), an aliphatic oxy group (eg, methoxy group, dodecyloxy group, etc.), an aromatic oxy group Groups (eg, 2,4-
Di-t-amylphenoxy group, 2-chlorophenoxy group, etc.), and aromatic group (for example, phenyl group).

As the aromatic group represented by R ₁₄ , the aromatic group described for R ₁ in the general formula [I] can be used.

The specific examples of the cyan dye-forming coupler represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

The cyan dye-forming coupler represented by the general formula [I] used in the present invention may be dispersed according to a known method and introduced into a silver halide color photographic light-sensitive material. In particular, phthalic acid esters and phosphoric acid After dissolving in a mixture of a high-boiling solvent such as esters and alkylphenols and a low-boiling solvent such as ethyl acetate, mixed with a gelatin solution containing a surfactant, a high-speed rotation mixer, a colloid mill,
It is preferable that the mixture is emulsified and dispersed using an ultrasonic disperser or the like and introduced into the photosensitive material.

The cyan dye-forming coupler represented by the general formula [I] used in the present invention may be used alone, or two or more cyan dye-forming couplers may be used in combination. Couplers other than the cyan dye-forming coupler represented by the general formula [I] may be used.

Next, the compound represented by formula (II) will be described.

[0050]

Embedded image

[In the formula, R ₂ represents a group other than hydrogen which can be substituted on a benzene ring, and n represents an integer of 1 to 5. Examples of the group that can be substituted on the benzene ring represented by R ₂ include a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, and aliphatic. Aromatic thio group, aromatic thio group, acyl group, acyloxy group,
Oxycarbonyl group, ureido group, carbonamide group,
Sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, nitro group, cyano group, halogen atom, amino group and the like, but an aliphatic group, an aromatic group,
Preferred are a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, a sulfonyl group, an oxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, and a sulfamoyl group.

As the preferred aliphatic group or aromatic group represented by R ₂ , the aliphatic group or aromatic group described for R ₁₄ in the general formula [VI] can be used.

The heterocyclic group represented by R ₂ is a 5- or 6-membered ring having at least one heteroatom selected from nitrogen, oxygen and sulfur, or a condensed ring of this ring with an aromatic ring or a heterocyclic ring And these may be further substituted with a suitable substituent. Specifically, for example, a pyridyl group, an imidazolyl group, a benzotriazolyl group, a piperazyl group, a piperidyl group, a pyrrolidyl group, a morpholyl group,
And a thiomorpholyl group.

A preferred aliphatic oxy group represented by R ₂ ,
As the aromatic oxy group, an aliphatic oxy group and an aromatic oxy group described for R ₁₃ and R ₁₄ in the general formula [VI] can be used.

Specific examples of other preferred R ₂ include a sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), an oxycarbonyl group (dodecyloxycarbonyl group, phenoxycarbonyl group, etc.), a carbonamide group (acetamide group, etc.), Sulfonamide groups (methanesulfonamide groups, p-toluenesulfonamide groups, etc.), carbamoyl groups (N, N-dimethylcarbamoyl groups, etc.),
And a sulfamoyl group (N, N-dimethylsulfamoyl group and the like).

Next, the compound represented by formula (III) will be described.

[0057]

Embedded image

[Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic group,
Or a heterocyclic group. As the aliphatic group represented by R ₃ , R ₄ , and R ₅ , a general formula [I
It can be used an aliphatic group described by R ₂ of I].
Preferred substituents on the aliphatic group include an aliphatic oxy group (methoxy group, dodecyloxy group, etc.), an aromatic oxy group (2,4-di-t-amylphenoxy group, 4-t-octylphenoxy group, etc.) ), Oxycarbonyl group (methoxycarbonyl group, dodecyloxycarbonyl group, phenoxycarbonyl group, etc.), aromatic group (phenyl group, etc.), heterocyclic group (piperidyl group, piperazyl group, etc.), acyloxy group (acetoxy group, benzoyloxy group) Group), a carbonamido group (such as an acetamido group), a sulfonamide group (such as a methanesulfonamide group, a p-toluenesulfonamido group), a carbamoyl group (such as an N, N-dimethylcarbamoyl group), and a sulfamoyl group (such as N, N -Dimethylsulfamoyl group, etc.), amino group (dimethylamino group, etc.), halogen atom, hydroxyl group And the like.

Examples of the aromatic groups represented by R ₃ , R ₄ and R ₅ include the aromatic groups described for R ₁ in the general formula [I].

Examples of the heterocyclic group represented by R ₃ , R ₄ and R ₅ include the heterocyclic group described for R ₂ in the general formula [II].

The compound represented by the general formula [II] or [III] used in the present invention may form a dimer or a multimer at a possible position. The case of forming a multimer is not limited to the aforementioned carbon number restriction.

Specific examples of the compound represented by the general formula [II] or [III] used in the present invention are shown below, but the present invention is not limited thereto.

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

The compound represented by the general formula [II] or [III] used in the present invention can be added to the same layer or a layer adjacent to the layer containing the cyan coupler according to the present invention. It is preferably added to the same layer, and it is particularly preferable to apply the composition after emulsifying and dispersing it together with the cyan coupler according to the present invention.

The amount of the compound represented by the general formula [II] or [III] used in the present invention ranges from 2% by weight (% by weight) of the cyan coupler (including the colored cyan coupler and the DIR compound) according to the present invention. 500 wt% is preferable, and more preferably 10 wt% to 300 wt%.

The compound represented by the general formula [II] or [III] used in the present invention may be a high-boiling organic solvent (e.g., phthalic acid ester,
Phosphoric acid esters, alkylphenols, etc.), and can be used in the same amount as the whole compound, or partially used in combination. The mixing ratio when used together can be used at any ratio. Further, the compounds represented by the general formula [II] or [III] used in the present invention may be used alone or in combination of two or more different compounds.

Next, the compound represented by formula (IV) will be described.

[0074]

Embedded image

[Wherein, R ₆ , R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an aliphatic group or an aromatic group;
Represents a hydrogen atom, a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, aliphatic or aromatic acyl group, aliphatic or aromatic oxycarbonyl group, and Z is

[0076]

Embedded image

Represents a non-metallic atomic group necessary for forming a 5- or 6-membered ring. The substituent represented by R ₆ , R ₇ , R ₈ and R ₉ is a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted substituted or unsubstituted group having 6 to 30 carbon atoms. A phenyl group is preferred. When R ₇ or R ₉ is an aliphatic group other than a methyl group or a phenyl group, it is preferable that both R ₆ and R ₈ are hydrogen atoms. In the present invention, R ₆ , R ₇ ,
It is particularly preferred that R ₈ and R ₉ are both hydrogen atoms or both are methyl groups.

Examples of the aliphatic group represented by Y include the aliphatic groups described for R ₂ in the general formula [II].

Examples of the aromatic group represented by Y include the aromatic groups described for R ₁ in the general formula [I].

Examples of the heterocyclic group represented by Y include the heterocyclic groups described for R ₂ in the general formula [II].

The aliphatic or aromatic acyl group represented by Y includes an acetyl group, a butylcarbonyl group, a hexadecylcarbonyl group, a benzoyl group and the like.

Examples of the aliphatic or aromatic oxycarbonyl group represented by Y include a methoxycarbonyl group, a dodecyloxycarbonyl group, a t-butyloxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl group and the like.

In particular, when R ₆ , R ₇ , R ₈ and R ₉ are all methyl groups, Y is preferably a hydrogen atom or a methyl group.

Further, Z, and

[0085]

Embedded image

Examples of the heterocyclic ring formed by the above include, for example, piperazine, piperidine, pyrrolidine, morpholine, 4-thiapiperidine, 4-thiapiperidine-4-oxide, 4-thiapiperidine-4,4-dioxide, piperidine-4 -One, piperazin-3-one and the like. These heterocycles may be substituted in addition to R ₆ , R ₇ , R ₈ , R ₉ , and Y. As the substituent, in addition to the substituents mentioned for Y, an aliphatic oxy group (for example, methoxy) Group, dodecyloxy group, etc.), aromatic oxy group (phenoxy group, etc.), acyloxy group (acetoxy group, benzoyloxy group, etc.), amino group (dioctylamino group, etc.) and the like.

Next, the compound represented by the formula [V] will be described.

[0088]

Embedded image

[Wherein, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic group, an aromatic group, or a heterocyclic group. R ₁₂ represents a group that can be substituted on a benzene ring, and m represents an integer of 0 to 5. As the aliphatic groups represented by R ₁₀ and R ₁₁ , those represented by the general formula [II]
And the aliphatic group represented (described) by R ₂ .

The aromatic groups represented by R ₁₀ and R ₁₁ include:
The aromatic group represented (described) by R ₁ in the general formula [I] can be exemplified.

As the heterocyclic groups represented by R ₁₀ and R ₁₁ ,
The heterocyclic group represented (described) by R ₂ in the general formula [II] can be exemplified.

The group which can be substituted on the benzene ring represented by R ₁₂ is represented by R ₂ of the general formula [II] (described).
Examples thereof include a group that can be substituted on a benzene ring.

The compound represented by the general formula [IV] or [V] used in the present invention may form a dimer or a multimer at a possible position. The case of forming a multimer is not limited to the aforementioned carbon number restriction.

The specific examples of the compound represented by the formula [IV] or [V] used in the present invention are shown below, but the present invention is not limited to these.

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

The compound represented by the general formula [IV] or [V] used in the present invention can be added to the same layer or a layer adjacent to the layer containing the cyan coupler according to the present invention. Preferably added to the same layer,
Further, it is particularly preferable to apply the composition after co-emulsifying and dispersing with the cyan coupler according to the present invention.

The amount of the compound represented by the general formula [IV] or [V] used in the present invention is from 1 mol% to 100 mol of the cyan coupler (including the colored cyan coupler and the DIR compound) according to the present invention. %, More preferably 5 mol% to 80 mol%.

The compounds represented by the general formula [IV] or [V] used in the present invention may be used alone or in combination of two or more different compounds.

The objective effects of the present invention are as follows: (at least one compound selected from the compound represented by the general formula [II] and the compound represented by the general formula [III]) and the compound represented by the general formula [IV] The use of at least one compound selected from the group consisting of a compound and at least one compound represented by the general formula [V]) can efficiently achieve the effect. And at least one selected from the compounds represented by the general formula [IV] and the compound represented by the general formula [V]. It is preferable to use them in combination.

In particular, the cyan dye-forming coupler represented by the general formula [I] has a partial structure represented by the general formula [VI], and a compound represented by the general formula [II]: II
When at least one selected from compounds represented by I] and (at least one selected from compounds represented by general formula [IV] and compounds represented by general formula [V]) are used, The maximum effect of the present invention can be obtained.

In the silver halide color photographic light-sensitive material of the present invention, the order of lamination of each photosensitive layer is not particularly limited, and various lamination orders can be adopted according to the purpose. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer can be laminated in this order from the support side, and conversely, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer in order from the support side. Can be laminated.

Further, the photosensitive layers having different color sensitivities may be interposed between two photosensitive layers having the same color sensitivity. For the purpose of improving color reproduction, a fourth or higher color-sensitive photosensitive layer may be provided in addition to the three layers of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer. The layer constitution using the fourth or higher color-sensitive photosensitive layer is described in JP-A-61-34541, JP-A-61-201245, JP-A-61-198236, JP-A-62-160448 and the like. These can be referred to.

In this case, the fourth or higher color-sensitive photosensitive layer may be disposed at any lamination position. Also, the fourth
Alternatively, the photosensitive layer having higher color sensitivity may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the respective light-sensitive layers and as the uppermost layer and the lowermost layer.

The non-photosensitive layers are described in JP-A-61-43.
No. 748, No. 59-113438, No. 59-1134
Couplers, DIR compounds, and the like described in JP-A Nos. 40-61, 61-20037, and 61-20038 may be contained, and a color-mixing inhibitor may be contained as usually used. These non-photosensitive layers are RD3
08119, p. 1002, section VII-K, and may be an auxiliary layer such as a filter layer or an intermediate layer.

Examples of the layer structure that can be employed in the light-sensitive material of the present invention include a forward layer, a reverse layer, and a unit structure described in RD308119, page 1002, section VII-K.

When there are two light-sensitive layers having the same color sensitivity, these light-sensitive layers may be the same, or may be a high-sensitivity emulsion layer as described in German Patent No. 923,045. It may have a two-layer structure of a low-sensitivity emulsion layer. In this case, it is usually preferable that the layers are arranged so that the sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the emulsion layers. Also, JP-A-57-112
No. 751, No. 62-200350, No. 62-2065
As described in JP-A Nos. 41 and 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 farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green sensitive layer (GH) / Low sensitivity green sensitive layer (GL) /
Installed in the order of high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH Can be mentioned.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH /
They can be arranged in the order of RH / GL / RL. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer / G
They may be arranged in the order of L / RL / GH / RH.

As described in JP-B-49-15495, three photosensitive layers having the same color sensitivity with different sensitivities were used.
Layers can be used. These three layers are arranged as a high-speed emulsion layer in the upper layer, a medium-speed emulsion layer in the middle layer, and a low-speed emulsion layer in the lower layer. Further, as described in JP-A-59-202264, a medium-speed emulsion layer, a high-speed emulsion layer, and a low-speed emulsion layer may be arranged in this order from the side away from the support.

In the case of three layers having different sensitivities, the order of lamination of these three layers is arbitrary. For example, the order of lamination is as follows: a high-speed emulsion layer, a low-speed emulsion layer, and a medium-speed emulsion layer. Or a low-speed emulsion layer, a medium-speed emulsion layer, and a high-speed emulsion layer. Further, four or more photosensitive layers having the same color sensitivity can be provided, and in this case, the arrangement is arbitrary as described above.

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

The silver halide emulsion in the present invention is described, for example, in RD17643, pp. 22-23 (Dec. 1978)
"I. Emulsion preparationan
dtypes), pp. 18716, 648, Grafkides, Physics and Chemistry of Photography, published by Paul Montell (P.
Glafkids; Chemic et Physi
que Photographique, Paul M
otel, 1967), Duffin, "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Photo).
optic Emulsion Chemist
ry, Focal Press, 1966), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press (VL Zelikman et al; Makin).
g and Coating Photographi
c Emulsion, FocalPress, 196
It can be prepared using the method described in 4). U.S. Pat. Nos. 3,574,628 and 3,663;
Monodisperse emulsions described in US Pat. No. 5,394 and British Patent 1,413,748 are also preferable.

Various photographic additives can be used in the silver halide emulsion before and after physical ripening or chemical ripening. Examples of the compound used in such a step include the aforementioned RD17643, pp. 23-27, 1871.
6,648-651 and 308119,996 II
Various compounds described in sections IA to 1011, section XX-B can be used.

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound which can react with formaldehyde described in 1,987 or 4,435,503 and can be immobilized.

The silver halide emulsion used in the present invention preferably contains silver iodobromide having an average silver iodide content of 4 to 20 mol%, and an average silver iodide content of 5 to 15 mol%. It is particularly preferred to contain silver iodobromide containing Further, silver chloride may be contained as long as the object of the present invention is not hindered.

In the present invention, when a silver halide emulsion containing silver halide grains formed by biasing the development start point to a specific portion of the surface of the silver halide grain and its vicinity is used, and other silver halide emulsions are used. The silver halide emulsions include those having regular crystals such as cubic, octahedral, and tetradecahedral, those having irregular crystal forms such as spheres, plates, and twin planes. It may have a crystal defect or a composite form thereof.

The silver halide grains other than those described above may be fine grains having a grain size of about 0.2 μm or less, large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. .

The silver halide emulsion used in the present invention is:
Research Disclosure (RD) 308
119 can be used. The places to be described are shown below.

[Item] [Page of RD308119] Iodine structure 993IA-A Manufacturing method 993IA and 994E Crystal habit normal crystal 994E Crystal habit twin crystal 994E epitaxial Epitaxial 994E Halogen composition uniformity Item 993I-B Item Halogen composition is not uniform 993I-B Item Halogen conversion 994I-C Halogen substitution 994I-C Item Containing metal 995I-D Monodispersion 995I-F Solvent addition 995I-F Item Latent image forming position surface 995I- Section G Inner Surface of Latent Image Forming Section 995I-G Section of Applicable Sensitive Material Negative 995I-H Section of Applicable Sensitive Material (Including Internal Fogging Particles) 995I-H Section Emulsion Used in Mixture 995I-J Section Desalting 995II-A Section In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. The additives used in such a process are RD17643, 1871
6 and 308119.

The following shows the places to be described.

[0130]

[Table 1]

Known photographic additives which can be used in the present invention are also described in the above RD. The relevant sections are described below.

[0132]

[Table 2]

Various color couplers can be used in the silver halide color photographic light-sensitive material of the present invention.

Examples of the yellow coupler include, for example, US Pat. Nos. 3,933,051, 4,022,620, 4,326,024, 4,401,752, and 4,248,961; JP-B-58-10739, British Patent Nos. 1,425,020 and 4,314,023
No. 4,511,649, European Patent 249,473
Those described in No. A or the like are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable. US Pat. Nos. 3,061,432, 3,725,067, 4,310,619 and 4,351. , 897, EP 73,636, Research Disclosure (hereinafter referred to as RD) 24220, 24230 (June 1984), JP-A-55-118034, and JP-A-60-335.
No. 52, No. 60-35730, No. 60-43659
No. 60-185951, No. 61-72238,
U.S. Pat. Nos. 4,500,630 and 4,540,654
No. 4,556,630, International Publication WO88 / 04
No. 795.

As the cyan coupler, a cyan coupler other than the cyan coupler represented by the general formula [I] of the present invention can be used in combination. Known cyan couplers include known phenol couplers and naphthol couplers. For example, U.S. Pat. Nos. 4,228,233 and 4,228.
296,200, 2,369,929, 2,8
10,171, 2,772,162, 2,89
5,826, 3,772,002, 3,75
8,308, 4,334,011, 4,32
7,173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Nos. 4,775,616 and 4,451,559
No. 4,427,767 and 4,690,889
Nos. 4,254,212 and 4,296,199
And those described in JP-A-61-42658 are preferred.

For the purpose of correcting unnecessary absorption of a coloring dye, a coupler described in US Pat. No. 4,744,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, and US Pat. , No. 120, it is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent as a leaving group.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent (Published) 3,234. No. 533 is preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,
No. 211, No. 4,367,282, No. 4,409,3
20 and 4,576,910, British Patent 2,10
2,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. A DIR coupler releasing a development inhibitor is disclosed in
Nos. 7-151944, 57-154234, 60
Nos. 184248, 63-37346, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent 2,097,1 discloses a coupler.
Nos. 40 and 2,131,188, JP-A-59-157.
Nos. 638 and 59-170840 are preferred.

Other couplers usable in the light-sensitive material of the present invention include those described in US Pat. No. 4,130,427.
No. 4,283,472.
No. 4,338,393, and 4,310,618, multi-equivalent couplers described in JP-A-60-185950.
Compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox compound described in JP-A-62-24252.
IR redox releasing redox compounds, EP 17
No. 3,302A, couplers capable of releasing a dye which becomes bicolor after release, RD11449, JP-A-24241, JP-A-61-61
Bleaching accelerator releasing couplers described in
Examples thereof include a ligand releasing coupler described in U.S. Pat. No. 4,553,477 and a leuco dye releasing coupler described in JP-A-63-75747.

Further, various couplers can be used in the present invention, and specific examples thereof are RD17643 described above.
VII-CF and RD308119, 1001-2
Page VII-DF.

The additive used in the present invention is RD3081
19, XIV, etc. can be added.

The support in the color light-sensitive material may be any one. In the case of a transparent support, a dye may be contained in the support for the purpose of preventing the light piping phenomenon (edge fog) that occurs when light enters the transparent support provided with the photographic emulsion layer from the edge. preferable. There is no particular limitation on the dye to be blended for such a purpose, but a dye having excellent heat resistance is preferable in the film forming process, and examples thereof include anthraquinone dyes. The color tone of the transparent support is preferably gray dyeing as seen in a general photosensitive material, and one or more dyes can be used in combination. SUMIPL manufactured by Sumitomo Chemical Co., Ltd.
AST, Diaresin, Bayer manufactured by Mitsubishi Kasei
Dyes such as MACROLEX manufactured by the company can be used alone or in an appropriate mixture.

The transparent support used in the present invention may be, for example, a copolymer polyester, or an antioxidant blended with the copolymer polyester as required, or a group consisting of sodium acetate, sodium hydroxide and tetraethylhydroxyammonium. After thoroughly drying the copolymerized polyester composition containing at least one selected, an extruder controlled to a temperature range of 260 to 320 ° C.,
The sheet is melted and extruded through a filter and a base, and the molten polymer is cooled and solidified on a rotating cooling drum to obtain an unstretched film. Thereafter, the unstretched film can be manufactured by biaxially stretching the film in the machine direction and the transverse direction, and heat-setting.

The stretching conditions of the film vary depending on the copolymer composition of the copolymerized polyester and cannot be uniformly defined. However, in the longitudinal direction, the stretching ratio is set within the temperature range from the glass transition temperature (Tg) of the copolymerized polyester to Tg + 100 ° C. 2.5 to 6.0 times, Tg + 5 ° C to Tg + 50 ° C in the horizontal direction
In the temperature range of 2.5 to 4.0 times.

The biaxially stretched film obtained as described above is usually heat-set at 150 to 240 ° C. and cooled. In this case, it may be relaxed in the vertical and / or horizontal direction if necessary.

The transparent support may be a single-layer film or sheet formed by the method described above.
Further, it may have a multilayer structure in which a film or sheet of another material and a film or sheet formed by the above method are laminated by a coextrusion method or a laminating method.

Although the thickness of the transparent support thus obtained is not particularly limited, it is usually 120 μm or less, preferably 40 to 120 μm, more preferably 50 to 120 μm.
110 μm. The local variation in the thickness of the transparent support is preferably within 5 μm, more preferably within 4 μm, and particularly preferably within 3 μm.

When the thickness of the transparent support is set within the above range, there is no problem in the strength and curl characteristics of the film after the photographic constituent layer is applied, and the thickness is within the range of the desired total film thickness. Can be. Further, when the thickness of the transparent support has a local variation of 5 μm or less, it is possible to prevent the occurrence of coating unevenness and drying unevenness when the photographic constituent layer is applied.

If necessary, a surface activation treatment such as corona discharge and / or an undercoat layer may be provided on the surface of the transparent support on the side on which the photographic constituent layer is to be formed, prior to the formation of the photographic constituent layer. be able to.

The undercoat layer is described in, for example, JP-A-59-1984.
19941, 59-77439, 59-224
No. 841 and Japanese Patent Publication No. 58-53029, etc., can be mentioned as suitable examples. The undercoat layer provided on the surface of the transparent support opposite to the photographic component layer is also called a back layer.

When the color light-sensitive material of the present invention is used in the form of a roll, it is preferable that the color light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, cartridges proposed in the following patents can be used.

Japanese Utility Model Laid-Open No. 58-67329 and 58-19
No. 5236, JP-A-58-181035, 58-1
No. 82634, U.S. Pat. No. 4,221,479, JP-A Nos. 1-231045, 2-170156 and 2-1.
No. 99451, No. 2-124564, No. 2-2014
No. 41, No. 2-205584, No. 2-210346
Nos. 2-211443, 2-214853, 2-264248, 3-37645, and 3-37
No. 646, U.S. Pat.
Nos. 8,693 and 4,832,275.

Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

To obtain a dye image using the color light-sensitive material of the present invention, a commonly known color development process is performed after exposure. That is, the aforementioned RD17643, pages 28 to 29, R
D18716, 647 and RD308119, 101
It can be developed by the usual method described on page 0, section XIX.

The light-sensitive material of the present invention includes, for example, the type / serial number, manufacturer name, emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. Magnetic recording for inputting various information required at the time, for example, various information obtained at the time of printing, such as the number of prints, selection of a filter, preference of a customer's color, size of a trimming frame, and other customer information. A layer may be provided.

In the present invention, the magnetic recording layer is preferably provided on the support on the side opposite to the photographic constituting layer, and the undercoat layer, the antistatic layer (conductive layer), It is preferable that a magnetic recording layer and a slip layer are formed.

As the magnetic fine powder used for the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. . Methods for producing these magnetic powders are known, and they can be produced according to known methods.

The optical density of the magnetic recording layer is preferably small in consideration of the influence on the photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by Konica Sakura Densitometer P
Using DA-65, using a filter that transmits blue light, light having a wavelength of 436 nm is vertically incident on the coating film,
According to a method of calculating light absorption by the coating film.

The magnetization amount of the magnetic recording layer per 1 m ² of the photosensitive material is preferably 3 × 10 ^-2 emu or more. The amount of magnetization was measured by using an external magnetic field of 1000 in a coating direction of a coating film having a fixed volume using a sample vibration magnetometer (VSM-3) manufactured by Toei Industry.
The magnetic flux density (residual magnetic flux density) when the external magnetic field is reduced to 0 after saturation once with oe is measured, and this is converted into the volume of the transparent magnetic layer contained per 1 m ² of the photographic photosensitive material. You can ask. If the amount of magnetization per unit area of the transparent magnetic layer is smaller than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is 0.01 to 20 μm.
m is preferred, more preferably 0.05 to 15 μm, and still more preferably 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins and the like are preferably used. It is also preferable to form a binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Further, it is necessary to adjust physical properties of these binders by curing with a curing agent, heat curing, electron beam curing, and the like. In particular, curing by adding a polyisocyanate-type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add nonmagnetic metal oxide particles, particularly alumina fine particles.

Examples of the support for the photosensitive material include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film, cellulose diacetate film, polycarbonate film, polystyrene film, polyolefin film and the like. it can.
In particular, JP-A-1-244446 and JP-A-1-291248.
No. 1-298350 No. 2-89045 No. 2
-93641, 2-181749, 2-214
When a polyester having a high water content as shown in JP-A Nos. 852 and 2-291135 is used, even if the support is thinned, the curl recovery property after the development processing is excellent.

In the present invention, the supports preferably used are PET and PEN. When these are used, the thickness is preferably 50 to 100 μm, particularly preferably 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ , T
iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It is preferable to have a conductive layer containing metal oxide particles such as O, BaO, and MoO ₃ , wherein the metal oxide particles contain oxygen vacancies and foreign atoms that form donors for the metal oxide used. Is generally preferred because of its high conductivity, and the latter is particularly preferred because it does not give fog to the silver halide emulsion.

As the binder for the conductive layer or the undercoat layer, the same binder as that for the magnetic recording layer can be used.

It is preferable to coat a higher fatty acid ester, a higher fatty acid amide, a polyorganosiloxane, a liquid paraffin, a wax or the like as a sliding layer on the magnetic recording layer.

When the light-sensitive material of the present invention is used as a roll-shaped color light-sensitive material, not only can the size of the camera and the cartridge be reduced, but also resources can be saved, and the storage space for the developed negative film can be saved. Is small, the film width is about 20 to 35 mm, preferably 20 to 35 mm.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² , preferably 400 to 600 mm ² , it is possible to make a small format without deteriorating the image quality of the final photographic print, and a smaller patrone and a smaller camera than before can be achieved. In addition, the aspect ratio of the shooting screen is not limited, and is not limited to the conventional 12 aspect ratio.
6 size 1: 1, half size 1: 1.4,135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that the light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, JP-A-58-67329, JP-A-58-195236, JP-A-58-181535, JP-A-58-182634,
U.S. Pat. No. 4,221,479, JP-A-1-23104
No. 5, 2-170156, 2-199451,
2-124564, 2-201441, 2-
No. 205843, No. 2-210346, No. 2-211
No. 443, No. 2-214853, No. 2-264248
Nos. 3-37645 and 3-37646; U.S. Pat. Nos. 4,846,418 and 4,848,693;
The cartridges proposed in JP-A-4,832,275 and the like can also be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

[0173]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 Evaluation of Single-Layer Sample (Preparation of Sample 101) On a triacetylcellulose film support having been subjected to a subbing treatment, layers having the following compositions were sequentially formed from the support side to form a single-layer sample. A color photographic light-sensitive material 101 was prepared.

Unless otherwise specified, the amount of addition refers to the number of grams per 1 m ² . Further, silver halide is shown in terms of silver, and sensitizing dye is shown in moles per mole of silver.

First layer: Red-sensitive layer Silver iodobromide emulsion (average grain size: 0.52 μm, silver iodide content: 8.0 mol%) 0.89 Silver iodobromide emulsion (average grain size: 0.38 μm, (Silver iodide content: 8.0 mol%) 0.22 sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye (SD- 3) 1.6 × 10 ^-4 cyan coupler (CR-2) 0.45 High boiling point solvent (Oil-1) 0.45 Gelatin 1.01 Second layer: protective layer Gelatin 1.01 The above composition Besides, a coating aid SU-1, a dispersion aid SU-4, a stabilizer ST-1, an antifoggant AF-1,
Hardener H-1 was added. The structure of the compound used in the above sample is the same as the compound used in Example 2.

(Preparation from Sample 102) Samples 102 to 102 were prepared in the same manner as Sample 101 except that the cyan coupler CR-2 of Sample 101 was changed as shown in Table 3 and the additives shown in Table 3 were added. 125 was created. When replacing the cyan coupler, it was replaced so as to be equimolar to CR-2 of Sample 101.

(Evaluation of Sensitivity and Color Development) Sample 10
Wedge exposure using white light is performed on each of Nos. 1 to 125, and development processing A ("normal processing") similar to Example 2 described later.
However, the development time was changed to 2:00 seconds. ), And measured with an optical densitometer (PDA-65, Konica Corporation) to determine its characteristic curve. From the characteristic curve of the cyan image, the logarithm of the reciprocal of the exposure amount giving the density of minimum density + 0.3 was determined as the photographic sensitivity. Further, the maximum cyan image density of each sample was obtained, and the color development was evaluated. The results are represented by the photographic sensitivity of the sample 101 and a relative value with the maximum density being 100 (reference).

(Evaluation of recolorability) Samples 101 to 1 prepared
25, the development processing B-1 ("fatigue bleaching liquid processing for single layer sample evaluation". The bleaching liquid was changed to the bleaching liquid B-1 formulation shown below, and the development time was 2 min. 3 hours
Processing was performed in the same manner as the developing processing A of Example 2 described later, except that the time was changed to 0 second. ), The density is measured immediately to obtain the characteristic curve of the cyan image so that the air oxidation of the leuco dye does not occur. Thereafter, a re-oxidation treatment is performed using the same re-oxidation treatment liquid C as in Example 2 described later, and the characteristic curve of the cyan image is obtained again. The color reproducibility is a ratio of the maximum density Dmax (B) of the cyan image before the re-oxidation processing to the maximum density Dmax (C) of the cyan image after the re-oxidation processing: Dmax (B) /
Dmax (C) x 100 (%) was evaluated.

(Development process B-1) From the development process A of Example 2 described later, the formulation of the bleach solution A was as follows.
Same as development process A, except that the formulation was changed, the development time was changed to 2,000 seconds, and the bleaching time was changed to 30 seconds.

<Preparation of bleaching solution B-1> To 360 ml of bleaching solution A used in the developing process A of Example 2 described later, 144 ml of the color developing solution similarly used in the developing process A and 396 water were used.
ml of sodium hydrosulfite, 9
Using 0% acetic acid and aqueous ammonia, set the potential to 30 mV, p
Adjust H to 5.

The sensitivity and sensitivity obtained for Samples 101 to 125
Table 3 summarizes the results of color development, color reproducibility, and color image fastness.

[0183]

[Table 3]

From the results shown in Table 3, it can be seen that the constitution of the present invention is effective as a means for improving the color reproducibility while maintaining the high sensitivity and high color developing property of the naphthol cyan coupler. Further, when the cyan coupler represented by the general formula (I) has a partial structure represented by the general formula (VI),
The effect is remarkable.

The cyan coupler represented by the general formula [I] has a partial structure represented by the general formula [VI], and comprises a compound represented by the general formula [II] and a compound represented by the general formula [III]. When at least one compound selected from the compounds represented by formula (IV) and (at least one compound selected from the compound represented by formula (IV) and the compound represented by formula (V)) are used in combination, It can be seen that the effect is particularly remarkable.

Example 2 Evaluation of Multilayer Sample (Preparation of Sample 201) On a triacetylcellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to form a multilayer color photographic light-sensitive material. A material sample 201 was produced.

[0187] The addition amount is particularly shows the number of grams per 1 m ² unless otherwise noted. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling organic solvent (Oil-1) 0.12 Gelatin 1.53 Second layer: Intermediate layer Antifouling agent (SC-1) 0.06 High-boiling organic solvent (Oil-2) 0.08 Gelatin 0.80 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion (average particle size 0.38 μm, iodine Silver iodide bromide emulsion (average grain size: 0.27 μm, silver iodide content: 2.0 mol%) 0.15 Sensitizing dye (SD-1) 8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-4 sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (CR-1) 0.56 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.02 High boiling point solvent (Oil-1) 0.49 Gelatin 1.14 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 0.52 μm, silver iodide content: 8.0 mol%) 89 silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 8.0 mol%) 0.22 sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye (SD-3) 1.6 × 10 ^-4 cyan coupler (CR-1) 0.45 colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0.017 High boiling point solvent (Oil-1) 0.39 Gelatin 1.01 Fifth layer: Highly sensitive red-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8.0 mol) %) 1.27 sensitizing dye (SD-1) 1.3 × 10 -4 sensitizing dye (SD-2) 1.3 × 10 -4 sensitizing dye (SD-3) .6 × 10 ^-4 Cyan coupler (CR-2) 0.20 Colored cyan coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High boiling solvent (Oil-1) 0.57 Gelatin 1 .10 sixth layer: middle layer color stain inhibitor (SC-1) 0.075 high boiling point organic solvent (Oil-2) 0.095 gelatin 1.00 seventh layer: middle layer gelatin 0.45 eighth layer: Low-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content: 8.0 mol%) 0.64 Silver iodobromide emulsion (average grain size: 0.27 μm, silver iodide content) 2.01 mol%) 0.21 sensitizing dye (SD-4) 7.4 × 10 ^-4 sensitizing dye (SD-5) 6.6 × 10 ^-4 magenta coupler (M-1) 0.19 magenta Coupler (M-2) 0.49 Colored magenta coupler (CM-1) 0.12 High Point solvent (Oil-2) 0.81 Gelatin 1.89 Ninth layer: Medium-sensitive green-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.76 Sensitizing dye (SD-6) 1.5 × 10 ^-4 sensitizing dye (SD-7) 1.6 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-4 magenta coupler (M- 1) 0.043 Magenta coupler (M-2) 0.10 Colored magenta coupler (CM-2) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.002 High boiling point solvent ( Oil-2) 0.37 Gelatin 0.76 10th layer: High-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8.0 mol%) 1.46 Sensitizing dye (SD-6) 0.93 × 10 -4 sensitizing dye (SD-7) 0.97 × 10 -4 sensitizing dye (SD-8 0.93 × 10 ^-4 Magenta coupler (M-1) 0.08 Magenta coupler (M-3) 0.133 Colored magenta coupler (CM-2) 0.014 High boiling solvent (Oil-1) 0.15 High Boiling point solvent (Oil-2) 0.42 Gelatin 1.08 Eleventh layer: Yellow filter layer Yellow colloidal silver 0.07 Color stain inhibitor (SC-1) 0.18 Formalin scavenger (HS-1) 0.14 High Boiling point solvent (Oil-2) 0.21 gelatin 0.73 12th layer: intermediate layer Formalin scavenger (HS-1) 0.18 gelatin 0.60 13th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average 0.073 silver iodobromide emulsion (average particle size 0.38 μm, silver iodide content 3.0 mol%) 0.16 iodobromide Silver emulsion ( Hitoshitsubu径0.27 [mu] m, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-9) 2.1 × 10 -4 Sensitizing dye (SD-10) 2.8 × 10 - ⁴ Yellow coupler (Y-1) 0.89 DIR compound (D-4) 0.008 High boiling solvent (Oil-2) 0.37 Gelatin 1.51 14th layer: Highly sensitive blue-sensitive layer Silver iodobromide emulsion (Average particle size: 1.00 μm, silver iodide content: 8.0 mol%) 0.95 Sensitizing dye (SD-9) 7.3 × 10 ^-4 Sensitizing dye (SD-10) 2.8 × 10 ^-4 Yellow coupler (Y-1) 0.16 High boiling point solvent (Oil-2) 0.093 Gelatin 0.80 15th layer: 1st protective layer Silver iodobromide emulsion (average particle size 0.05 μm, iodide (Silver content: 3.0 mol%) 0.30 UV absorber (UV-1) 0.094 UV absorber (UV-2) 0.10 Formali Scavenger (HS-1) 0.38 High boiling solvent (Oil-1) 0.10 Gelatin 1.44 16th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.55 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, hardener H-1, H-
2. Viscosity modifier, stabilizer ST-1, dye AI-1, AI
-2, antifoggant AF-1, weight average molecular weight: 10,
000 and weight average molecular weight: 100,000 of two kinds of polyvinylpyrrolidone (AF-2) and preservative DI-1
Was added. The amount of DI-1 added was 9.4 mg / m ² .

The structures of the compounds used in the above samples are shown below.

[0190]

Embedded image

[0191]

Embedded image

[0192]

Embedded image

[0193]

Embedded image

[0194]

Embedded image

[0195]

Embedded image

[0196]

Embedded image

[0197]

Embedded image

(Preparation of Samples 202 to 225) Sample 201
Sample 2 was obtained except that the cyan coupler CR-2 of the fifth layer was changed as shown in Table 4 and the additives shown in Table 4 were added.
Samples 202 to 225 were prepared in the same manner as in Sample No. 01. Fifth
When replacing the coupler of the layer, the CR of the sample 201 is used.
It was replaced so as to be equimolar to -2.

(Evaluation of Sensitivity and Coloring Property) Sample 20
After performing wedge exposure using white light on each of Nos. 1 to 225, a developing process A (that is, "normal process") described below is performed, and then an optical densitometer (PDA-65 type, Konica Corporation).
And the characteristic curve was obtained. From the characteristic curve of the cyan image, the logarithm of the reciprocal of the exposure amount giving the density of minimum density + 0.3 was determined as the photographic sensitivity. Further, the maximum cyan image density of each sample was obtained, and the color development was evaluated. The results were obtained by setting the photographic sensitivity of sample 201 and the maximum density to 10
It is represented by a relative value of 0 (reference).

(Evaluation of recolorability) Samples 201 and 2 prepared
25, wedge exposure using white light, and then processing B-2 described below (ie, "fatigue bleaching liquid processing for evaluation of multilayer sample"; After performing the same processing as the development processing A), the density measurement is immediately carried out to obtain the characteristic curve of the cyan image so that the air oxidation of the leuco dye does not occur. Thereafter, a re-oxidation treatment (using the re-oxidation treatment liquid C) described below is performed, and a characteristic curve of the cyan image is obtained again. The color reproducibility is the maximum density Dmax (B) of the cyan image before the re-oxidation processing with respect to the maximum density Dmax (C) of the cyan image after the re-oxidation processing.
Ratio: Dmax (B) / Dmax (C) × 100 (%)
Was evaluated.

(Evaluation of Color Image Fastness) The evaluation of color image fastness was carried out after wedge exposure using white light, followed by development processing A.
(I.e., the "normal processing") and the sample for which the characteristic curve of the cyan image has been obtained are subjected to a light resistance evaluation light source (xenon tester: 1).
(100,000 lux) for 7 days, the residual ratio (%) of the cyan image was determined.

<< Development Processing A >> (Processing Step) Process Processing Time Processing Temperature Replenishment Amount * Color Development 3 min 15 sec 38 ± 0.3 ° C. 780 ml Bleaching 45 sec 38 ± 2.0 ° C. 150 ml Fixing 1 min 30 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

<Preparation of Processing Agent> (Composition of Color Developing Solution) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Finish to 2.0 liters and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and potassium hydroxide or 20% sulfuric acid was used. Adjust to pH 10.18.

(Bleach A composition) Water 700 ml 1,3-diaminopropanetetraacetate ammonium iron (III) 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Adjust to pH 4.4 using aqueous ammonia or glacial acetic acid.

(Composition of bleaching replenisher) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 using aqueous ammonia or glacial acetic acid.

(Fixing Solution Formulation) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water was added to make up to 1.0 liter, and the pH was adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 using aqueous ammonia or glacial acetic acid. .

(Preparation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make up to 1.0 liter, and adjust to pH 8.5 using ammonia water or 50% sulfuric acid.

<< Development B-2 >> Bleaching solution A of development A
Same as development processing A except that the formulation was changed to the following bleaching solution B-2 formulation.

(Bleach B-2 Formulation) Bleach A: 6
After adding 333 ml of pure water to 67 ml, 90% acetic acid is added to adjust the pH to 4.25. Next, sodium hydrosulfite was added to adjust the ferrous ion concentration to 12.5 g.
After that, the pH is readjusted to 4.25 using aqueous ammonia.

<< Reoxidation Treatment C >> (Reoxidation treatment liquid C formulation) Iron ethylenediaminetetraacetate (II
I) Water is added to 150 g of ammonium to make up to 1.0 liter, and the pH is adjusted to 6.0 using aqueous ammonia.

Table 5 shows the results of the sensitivities, color developing properties, color reproducibility, and color image fastness obtained for the samples 201 to 225.

[0214]

[Table 4]

[0215]

[Table 5]

As is clear from the results shown in Tables 4 and 5, the sample of the present invention was obtained while maintaining high sensitivity and high color development.
It can be seen that the color reproduction failure is improved and the color image is excellent in fastness.

It is also found that when the compound represented by the general formula [I] has a partial structure represented by the general formula [VI], remarkably excellent performance is obtained.

Also, (at least one selected from the compound represented by the general formula [II] and the compound represented by the general formula [III]) and the compound represented by the general formula [IV] and the compound represented by the general formula [ V] at least one compound selected from the group consisting of:
It can be seen that a remarkable improvement effect can be obtained when the (type) is used in combination.

Example 3 Evaluation of Multilayer Sample The present invention was applied not only to the fifth-layer cyan coupler CR-2 as in Example 2, but also to the third-layer and fourth-layer cyan coupler CR-1. (Chemical dye-forming coupler represented by the general formula [I]) and (at least one selected from the compound represented by the general formula [II] and the compound represented by the general formula [III]) and ( The same evaluation as in Example 2 was performed by adding at least one member selected from the group consisting of the compound represented by the formula [IV] and the compound represented by the general formula [V]. As a result, Example 2
Similarly, significant improvements were obtained in sensitivity, color development, color reproducibility, and color image fastness.

[0220]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material having a small decrease in cyan image density even when processed using a bleaching solution or a bleach-fixing solution which is firstly exhausted. .

Second, a silver halide color photographic light-sensitive material having high sensitivity and high color development and excellent color reproducibility could be provided.

Third, a silver halide color photographic light-sensitive material excellent in the fastness of a cyan image could be provided.

Claims (2)

[Claims] A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, comprising a cyan dye-forming coupler represented by the following general formula [I]: And [(at least one selected from the compounds represented by the following general formula [II] and the compounds represented by the general formula [III]) and (the following general formula [I
V] and at least one member selected from compounds represented by the general formula [V]). Embedded image [In the formula, R ₁ represents a substituted or unsubstituted aromatic group, an aliphatic group, or a heterocyclic group, and X represents a hydrogen atom or an aromatic primary amine, which is removed by a coupling reaction with an oxidized developing agent. Represents a possible group. [Chemical formula 2] [In the formula, R ₂ represents a group that can be substituted on a benzene ring other than a hydrogen atom, and n represents an integer of 1 to 5. When n is 2 or more, R ₂ may be the same or different. [Chemical formula 3] Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom,
Represents a substituted or unsubstituted aliphatic group, aromatic group, or heterocyclic group. [Formula 4] [Wherein, R ₆ , R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an aliphatic group, or an aromatic group, Y represents a hydrogen atom,
Represents a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, aliphatic or aromatic acyl group, aliphatic or aromatic oxycarbonyl group, and Z is Represents a group of nonmetallic atoms necessary to form a 5- to 6-membered ring together with [Formula 6] [Wherein, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic group, an aromatic group, or a heterocyclic group, and R ₁₂ represents a group that can be substituted on a benzene ring. , M
Represents an integer of 0 to 5. When m is 2 or more, R ₁₂ may be the same or different. ] 2. The silver halide color photographic material according to claim 1, wherein in the general formula [I], R ₁ is represented by the following general formula [VI]. Embedded image Wherein R ₁₃ is a halogen atom, substituted or unsubstituted,
Represents an aliphatic oxy group or an aromatic oxy group, R ₁₄ represents a substituted or unsubstituted aliphatic group, an aromatic group, an aliphatic oxy group, or an aromatic oxy group, and k is an integer of 1 to 4. Represent. ]