JP2001356456A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material excellent in color reproducibility and giving an image having improved preservability, particularly such improved image stability as not to cause unfavorable stain under irradiation with light. SOLUTION: In the silver halide photographic sensitive material with at least one silver halide emulsion layer on the base, at least one silver halide emulsion layer contains one or more of two-equivalent cyan dye forming couplers of formulae (C-l) and (C-2) and further contains a compound of formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a "light-sensitive material"), and more particularly to a halogen dye having excellent fastness, image stability and color reproducibility of a dye image obtained. It relates to a silver halide photographic material.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials have been widely used as materials for providing high-quality images at low cost and with stable quality. Is growing more and more. Improvements in color reproducibility, gradation reproducibility, sharpness, etc. are required to meet the demand for high image quality. Therefore, it is necessary to improve stability during storage with time, performance variability during development processing, and the like. Furthermore,
There is also a demand for high robustness of the obtained images.

To meet the demand for higher image quality, pyrazolotriazole-based cyan dye-forming couplers have been proposed which have improved the absorption characteristics of conventional phenolic or naphthol-based cyan dye couplers. Image dyes formed from triazole-based cyan dye-forming couplers suffer from poor lightfastness.

[0004] For this purpose, an improvement technique using a dye image stabilizer has been studied. For example, a phenolic compound described in JP-A-9-50101 and the like, 9-23055
No. 3 amine-based or phenyl ether-based compounds.

However, when these techniques are used, the discoloration of an image dye formed from a pyrazolotriazole-based cyan dye-forming coupler by light is improved, but the generation of stain by light is reduced by a conventional phenol or naphthol type. The problem of an increase with respect to cyan dye couplers has been newly found, and it has been found that, in particular, the generation of stain by light is remarkably increased in a four-equivalent pyrazolotriazole-based cyan dye-forming coupler.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide excellent color reproducibility and storage stability of an obtained image, especially under light irradiation. Another object of the present invention is to provide a silver halide light-sensitive material having improved image stability without generating undesirable stains.

[0007]

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

[0008] 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the formulas (C-1) and (C-2). Characterized in that the silver halide emulsion layer containing at least one or more bi-equivalent cyan dye-forming couplers and a compound represented by formula (1) above. Silver halide photographic material.

[0009] 2. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the formulas (C-1) and (C-2). Characterized in that the silver halide emulsion layer containing at least one or more bi-equivalent cyan dye-forming couplers and a compound represented by formula (2) above. Silver halide photographic material.

[0010] 3. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the formulas (C-1) and (C-2). Wherein the silver halide emulsion layer containing at least one kind of the bi-equivalent cyan dye-forming coupler is a compound represented by the above general formula (3) or (4). A silver halide photographic light-sensitive material comprising:

4. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a compound represented by the above formula (1) and a compound represented by the following formula (2). A silver halide photographic light-sensitive material comprising the compound represented by the formula (I) in the same layer.

5. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a compound represented by the above formula (1), and A silver halide photographic light-sensitive material comprising at least one compound represented by the above formula (3) or (4) in the same layer.

6. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the formula (C-1) or (C-2). The compound represented by the above general formula (1) in the same layer, and the compound represented by the above general formula (2) in the same layer. A silver halide photographic material.

7. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the formula (C-1) or (C-2). And at least one compound represented by the general formula (1) in the same layer, and represented by the general formula (3) or (4) in the same layer. Silver halide photographic material comprising at least one compound selected from the group consisting of:

Hereinafter, the present invention will be described in more detail. In the present invention, the cyan dye-forming coupler represented by the general formulas (C-1) and (C-2) (hereinafter, the cyan dye-forming coupler is also simply referred to as cyan coupler) will be described.

In the above general formulas (C-1) and (C-2), the branched alkyl groups represented by R ₃ , R ₄ , R ₇ and R ₈ include i-propyl, t-butyl and sec- Butyl,
i-butyl, t-octyl and the like.

The alkyl component of the substituted alkyl group includes:
It may be linear, branched or cyclic, and may be methyl, ethyl,
Butyl, i-propyl, t-butyl, sec-butyl,
i-butyl, t-octyl, cyclohexyl and the like.

The aryl component of the substituted aryl group includes
Phenyl and the like. Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-imidazolyl, 2-thiazolyl, 3-isoxazolyl, 3-pyridyl, 2-pyridyl, 2-pyrimidyl, 3-pyrazolyl, and 2-benzothiazolyl. Can be mentioned.

However, when R ₃ , R ₄ , R ₇ , and R ₈ represent a substituted alkyl group or a substituted aryl group, these alkyl and aryl components necessarily have a substituent.

When R ₃ , R ₄ , R ₇ and R ₈ represent a branched alkyl group or a heterocyclic group, these groups may have a substituent, if necessary.

These substituents are not particularly limited, but typically include groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hetero Examples include groups such as ring thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues. These groups may be further substituted by the above substituents.

In the general formulas (C-1) and (C-2), the substituents represented by R ₂ and R ₆ are not particularly limited, but are typically alkyl, aryl, anilino, acylamino, sulfonamide, Examples include alkylthio, arylthio, alkenyl, and cycloalkyl groups.In addition, halogen atoms and cycloalkenyl, alkynyl, heterocycles, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hetero Examples include groups such as ring thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues.

The substituents on the branched alkyl group, substituted alkyl group, substituted aryl group or heterocyclic group represented by R ₃ , R ₄ , R ₇ and R ₈ , and represented by R ₂ and R ₆ In the substituent, the alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group is preferably a phenyl group. Examples of the acylamino group include an alkylcarbonylamino group and an arylsulfonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the alkyl group and the aryl group in the substituents represented by R ₂ and R ₆ , respectively.

The alkenyl group is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched.

The cycloalkenyl group may have 3 to 3 carbon atoms.
12, especially 5-7 are preferred.

Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group;
As a phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; as an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; as a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group An sulfosyl group such as an alkylsulfamoyl group and an arylsulfamoyl group; an acyloxy group such as an alkylcarbonyloxy group and an arylcarbonyloxy group; a sulfonyloxy group such as an alkylsulfonyloxy group and an arylsulfonyloxy group; A carbamoyloxy group such as an alkylcarbamoyloxy group or an arylcarbamoyloxy group; a ureido group such as an alkylureido group or an arylureido group; a sulfamoylamino group An alkylsulfamoylamino group, an arylsulfamoylamino group or the like; a 5- to 7-membered heterocyclic group is preferable, and specific examples thereof include 2-furyl, 2-thienyl, 2-pyrimidyl, Benzothiazole, 1-pyrrolyl, 1-tetrazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, and for example, 3,4,5,6-tetrahydropyranyl-2
-Oxy, 1-phenyltetrazol-5-oxy group and the like; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio, 2-benzothiazolylthio, 2,4-diphenoxy. -1,3,5-triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide, 3-heptadecylsuccinimide group, phthalimide group and glutar Imido group or the like; spiro compound residue as spiro [3.
3] heptane-1-yl and the like. Examples of the bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl,
7,7-dimethyl-bicyclo [2.2.1] heptane-
1-yl and the like.

As the substituent represented by R ₂ and R ₆ , an alkyl group and an aryl group are preferable, and an aryl group is particularly preferable.

The above-mentioned groups may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

Examples of atoms and groups which can be eliminated by reaction with the oxidized form of the color developing agent represented by X ₁ and X ₂ include, for example, a halogen atom (chlorine, bromine, fluorine, etc.) and an alkoxy group (methoxy, ethoxy, propyloxy). , Pentyloxy,
Cyclopentyloxy, hexyloxy, cyclohexyloxy, octyloxy, dodecyloxy, etc., aryloxy group (phenoxy, naphthyloxy, etc.), heterocyclic oxy group (pyridyloxy, thiazolyloxy, oxazolyloxy, imidazolyloxy, furyloxy,
Pyrrolyloxy, pyrazinyloxy, pyrimidinyloxy, pyridazinyloxy, selenazolyloxy, sulfolanyloxy, piperidinyloxy, pyrazolyloxy, tetrazolyloxy, etc.), acyloxy group (acetyloxy, ethylcarbonyloxy, butylcarbonyloxy) Octylcarbonyloxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.), sulfonyloxy group, alkoxycarbonyloxy group (methoxycarbonyloxy, ethoxycarbonyloxy, etc.), aryloxycarbonyloxy group (phenyloxycarbonyloxy, etc.), alkyloxalyl Oxy group, alkoxyoxalyloxy group, alkylthio group (methylthio, ethylthio, etc.), arylthio group (phenylthio,
Naphthylthio, etc.), heterocyclic thio group (pyridylthio, furylthio, etc.), alkyloxythiocarbonylthio group, acylamino group (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, -Ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc., sulfonamide group (methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, hexylsulfonylamino, cyclohexylsulfonylamino, octylsulfonylamino , Dodecylsulfonylamino, phenylsulfonylamino, etc.), nitrogen-containing nitrogen-bonded Heterocyclic group, an alkyloxycarbonyl group, an aryloxycarbonylamino group include the group such as a carboxyl group.

The substituent of X ₁ and X ₂ is preferably an aryloxy group. General formulas (C-1) and (C-
Of the cyan couplers represented by 2), those represented by general formula (C-1) are preferred.

More preferably, the following general formula (C-1A)
Or (C-1B).

[0035]

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In the formula, R ₉ represents a substituent, and the substituent represented by R ₉ is not particularly limited, but is typically an alkyl, a halogen atom, an alkoxy, an aryloxy, a sulfonyl, an alkylthio, an arylthio, a dialkylamino. ,
Each group includes acylamino, sulfonamide and the like.
n represents the integer of 0-2.

[0037]

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In the formula, R ₁₀ represents a substituent, and the substituent represented by R ₁₀ is not particularly limited.
Halogen atom, alkoxy, aryloxy, sulfonyl, alkylthio, arylthio, dialkylamino,
Each group includes acylamino, sulfonamide and the like.
Preferably, R ₁₀ is a halogen atom, an alkoxy or an aryloxy group. n represents the integer of 0-2.

The following formulas (C-1) and (C-2)
The following are specific compounds of the cyan coupler (referred to as the cyan coupler of the present invention) represented by the following formula, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The cyan coupler of the present invention is generally used in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-3 mol per mol of silver halide.
It can be used in the range of 10 ^-2 to 8 × 10 ^-1 mol.

Next, the compound represented by formula (1) will be described. In the general formula (1), R ₁₁ represents an alkyl group or a trialkylsilyl group, and R ₁₂ , R ₁₃ , R
₁₄ , R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkenyloxy group, an acylamino group, a halogen atom, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an acyloxy group. Represents a group, an acyl group, a trialkylsilyloxy group or a sulfonamide group. R ₁₁ and R
Two of the ₁₆ groups may be linked to form a 5- to 6-membered ring.

In the general formula (1), R ₁₂ , R ₁₃ , R ₁₄ ,
Examples of R ₁₅ and R ₁₆ include a hydrogen atom, an alkyl group (eg, methyl, ethyl, octyl, lauryl, etc.), an alkoxy group (eg, phenyl, naphthyl, etc.), an aryloxy group (eg, phenoxy, naphthoxy, etc.), alkenyl Group (eg, octenyl), alkenyloxy (eg, octenyloxy), acylamino group (eg, acetylamino, palmitoylamino, benzoylamino, etc.), halogen atom (eg, chlorine, bromine, etc.), alkylthio group (eg, octylthio, laurylthio, etc.) ), An arylthio group (eg, phenylthio), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, hexadecyloxycarbonyl, etc.), an acyloxy group (eg, acetyloxy, benzoyloxy, etc.), an acyl group (eg, acetyl Le, valeryl, stearoyl, benzoyl, etc.), a sulfonamido group (e.g., octyl sulfonamide, lauryl sulfonamide), trialkylsilyl group (e.g. dimethylpropyl silyloxy, etc.).

Further, two groups out of R _{11 to} R ₁₆ may be linked to form a 5- to 6-membered ring (for example, an indane, spiroindane, chroman, spirochroman ring). In the general formula (1), R ₁₃ and R ₁₅ are preferably not alkoxy groups.

A preferred compound in the general formula (1) is represented by the following general formula (1A).

[0072]

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In the formula, R ₁₇ , R ₁₈ , R ₁₉ and R ₁₁₀ represent an alkyl group. More preferably, it is a compound of the general formula (1A) in which both R ₁₇ and R ₁₈ have 5 or less carbon atoms.

Typical specific examples of the compound represented by the general formula (1) include compounds III-1 to III-19 described in JP-A-9-230553, but the present invention is not limited thereto. Not something.

The compound represented by formula (1) of the present invention can be used in an amount of usually 1 × 10 ⁻³ to 10 mol, preferably 1 × 10 ⁻² to 1 mol, per 1 mol of the coupler. .

Next, the compound represented by formula (2) will be described. In the general formula (2), R ₂₁ is a substituent having a carbon unsaturated bond and having 11 to 30 carbon atoms, and preferably a substituent having 15 to 25 carbon atoms.

The specific examples of the compounds represented by formula (2) are shown below, but the present invention is not limited thereto. _{2-1 (CH 3) 4 C =} CH (CH 2) 4 C (CH 3) = CHCH 2
_{OH 2-2 CH 3 CH = CH (} CH 2) 3 CH = CH (CH 2) 5 CH 2
_{OH 2-3 CH 3 CH 2 CH =} CH (CH 2) 11 CH 2 OH 2-4 CH 3 (CH 2) 5 CH = CH (CH 2) 5 CH 2 OH 2-5 CH 3 (CH 2) 10 _{CH = CHCH 2 CH 2 OH 2-6} CH 3 CH (CH 3) CH = CHCH = CH (CH 2) 8 C
_{H 2 OH 2-7 CH 3 (CH} 2) 5 CH = CHCH 2 CH = CH (CH 2) 3
_{CH 2 OH 2-8 CH 3 (CH} 2) 2 CH = CH (CH 2) 8 CH 2 OH 2-9 CH 3 (CH 2) 7 CH = CH (CH 2) 5 CH 2 OH 2-10 CH 3 _{(CH 2) 5 CH = CH} (CH 2) 7 CH 2 OH 2-11 CH 3 CH = CH (CH 2) 11 CH 2 OH 2-12 CH 2 = CH (CH 2) 16 CH 2 OH 2-13 CH ₃ (CH ₂ ) ₁₁ CH (OH) CH ＝ CH ₂ 2-14 CH ₃ (CH ₂ ) ₇ CH ＝ CH (CH ₂ ) ₇ OH The compound represented by the general formula (2) of the present invention is usually It can be used in a weight ratio of 1 × 10 ⁻² to 10 and preferably 1 × 10 ^{−1 to} 3 with respect to the coupler.

Next, the compound represented by formula (3) or (4) will be described. In the general formulas (3) and (4), the substituents represented by R ₃₁ and R ₄₁ are not particularly limited, but are each a hydrogen atom, an alkyl group, an alkoxy group,
Aryl group, aryloxy group, alkenyl group, alkenyloxy group, acylamino group, halogen atom, alkylthio group, arylthio group, alkoxycarbonyl group,
Represents an acyloxy group, an acyl group, a trialkylsilyloxy group or a sulfonamide group.

The preferred compound in the general formula (3) or (4) is represented by the following general formula (3A) or (3B).

[0080]

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Wherein R ₃₃ and R ₃₄ are each an alkyl group,
Represents an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkenyloxy group, an acylamino group, a halogen atom, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a trialkylsilyloxy group or a sulfonamide group .

The following are typical examples of the compound represented by formula (3) or (4), but the present invention is not limited thereto.

[0083]

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The compounds represented by formulas (3) and (4) of the present invention are usually used in a weight ratio of 1 × 10 5
^-2 to 10, preferably 1 × 10 ^{−1 to} 3 can be used.

The cyan coupler of the present invention can be used in combination with other types of cyan coupler as long as the effects of the present invention are not impaired.

A hydrophobic compound such as a dye-forming coupler or a dye image stabilizer is usually mixed with a high-boiling organic solvent having a boiling point of about 150 ° C. or more or a water-insoluble polymer compound, and then dissolved by heating to 80 ° C. or more. Or, if necessary, a low boiling organic solvent (such as ethyl acetate) and / or a water-soluble organic solvent are used in combination and dissolved, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution using a stirrer, a homogenizer, After emulsifying and dispersing using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, it may be added to the target hydrophilic colloid layer. When a low-boiling organic solvent is used, it is preferable to include a step of removing the low-boiling organic solvent after or at the same time as emulsification and dispersion.

Examples of the high-boiling organic solvent used include esters such as phthalic acid esters, phosphoric acid esters and aliphatic esters, higher saturated or unsaturated alcohols, alkylphenols, organic acid amides, ketones, hydrocarbon compounds and the like. Is mentioned.

Examples of these are described in, for example,
Exemplified Compounds A-1 to 196048 on pages 4 to 7
A-120, Exemplified compounds II-1 to II- described on pages 8 to 9
Exemplified compounds H-1 to H-2 described on pages 29 and 14 to 15
2. Exemplified compounds S-1 to S-69 described on pages 3 to 7 of JP-A-1-209446 and JP-A-63-253943.
Exemplified compounds I-1 to I-95 described on pages 0 to 12, U.S. Pat. No. 5,429,913 Exemplified compounds (aI) to (a-IX) described on page 2 right, and EP 550,359 A1.
No. 22 to page 5, exemplified compounds 5-1 to 5-15.

The composition of the silver halide photographic emulsion used in the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chloroiodobromide, silver chloroiodide and the like. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. From the viewpoint of rapid processing property and processing stability, preferably 97 mol% or more,
More preferably, a silver halide emulsion containing 98 to 99.9 mol% of silver chloride is preferred.

For obtaining a silver halide emulsion used in the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing silver bromide at a high concentration may be epitaxy-bonded to silver halide emulsion grains, may be a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. May simply have regions with different compositions. Further, the composition may be changed continuously or discontinuously.
It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

For obtaining a silver halide emulsion, it is advantageous to include a heavy metal ion. Heavy metal ions that can be used for such purposes include iron, iridium,
Platinum, palladium, nickel, rhodium, osmium,
Examples thereof include Group 8 to 10 metals such as ruthenium and cobalt, Group 12 transition metals such as cadmium, zinc and mercury, and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex,
Examples of the ligand or ion include cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to incorporate heavy metal ions into the silver halide emulsion, the heavy metal compound is added to the silver halide emulsion during the physical ripening before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is from 1 × 10 ^-9 to 1 mol / mol of silver halide.
1 × 10 ⁻² mol is preferred, and especially 1 × 10 ^{−8 to} 5 × 10
^-5 mol is preferred.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,22;
5,666, JP-A-55-26589, and JP-B-55-55.
No. 42737 and the Journal of Photographic Science (J. Photogr. Sc.
i. ) Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be produced and used by methods described in documents such as 21, 39 (1973). Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, and more preferably 0.2 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. The range is 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains used in the present invention is preferably a monodisperse silver halide grain having a variation coefficient of 0.22 or less, more preferably 0.15 or less, and particularly preferably a variation coefficient. That is, two or more monodisperse emulsions having a coefficient of 0.15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (S: standard deviation of particle size distribution, R: average particle size) The particle size referred to here is the diameter of a spherical silver halide particle, or a cubic or spherical particle. In the case of particles having shapes other than, the diameter represents a diameter when the projected image is converted into a circular image having the same area.

As a device and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion used in the present invention is:
It may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at a time, or may be grown after seed particles have been produced. The method of producing the seed particles and the method of growing may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used. Also, JP-A-57-92523 and JP-A-57-9
No. 2524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in DE-A-2,921,164. Apparatus for continuously changing the concentration of a salt and a water-soluble halide salt aqueous solution, JP-B-56-5
No. 01776 or the like, a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form a grain while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As a chalcogen sensitizer that can be used, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.
The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect size, and the like.
In the range of 10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^-5 mol
The range is preferably from ^{-8 to} 3 x ^10-5 mol.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1 × 10
^-8 mol.

The chemical sensitization of a silver halide emulsion includes the following.
A reduction sensitization method may be used. For the silver halide emulsion, known antifoggants and stabilizers are used for the purpose of preventing fog generated during the preparation process of the photosensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. I can do it. Examples of preferred compounds that can be used for such purposes include the compounds represented by the general formula (II) described in the lower column of page 7 of JP-A-2-14636, and more preferred specific compounds Are (IIa-1) to (IIa-8) and (IIa-8) described on page 8 of the publication.
Compounds b-1) to (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4
-Ethoxyphenyl) -5-mercaptotetrazole and the like.

These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, finishing the chemical sensitizing step, and preparing a coating solution. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ⁻² mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-5 to 1 × 10 ¹ mol. ^-2 mol is more preferred. Also, when added to a layer other than the silver halide emulsion layer, the amount in the coating film is, 1 m ² per 1 × 10 ^-9 ~1 ×
An amount of about 10 ^-3 mol is preferred.

As the light-sensitive material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. -3770
The dyes described in the above are preferably used. As the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are preferable. It is preferable because it has characteristics and does not affect the photographic characteristics of the silver halide emulsion and does not cause contamination due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication.

For the purpose of improving sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferably an amount that makes the spectral reflection density 0.7 or more, and more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the light-sensitive material of the present invention is used as a color photographic light-sensitive material, 400 to 900 n in combination with a yellow coupler, a magenta coupler and a cyan coupler.
It has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the m wavelength range. The silver halide emulsion may be of one type or two types.
It contains a combination of two or more sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion, any known compounds can be used.
As the blue-sensitive sensitizing dye, BS-1 to 8 described in JP-A-3-251840, page 28, can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described on pages 6 to 8 are preferably used. Further, these infrared, red, green, and blue light-sensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. No. 1
It is preferable to use compounds S-1 to S-17 described on pages 5 to 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. As a method of adding the sensitizing dye, methanol, ethanol, fluorinated alcohol, acetone, may be dissolved in water-miscible organic solvents such as dimethylformamide or water and added as a solution, or added as a solid dispersion. Is also good.

The cyan dye-forming coupler of the present invention is used in the emulsified dispersion and the light-sensitive material of the present invention. However, other dye-forming couplers may be used in combination, or other dye-forming couplers may be used. It may be used in a photographic component layer different from the silver halide emulsion layer containing the emulsified dispersion using the dye-forming coupler of the present invention. These are included, and the dye-forming coupler used in the present invention has a wavelength range of 400
Yellow dye-forming coupler having a spectral absorption maximum wavelength of ~ 500 nm, magenta dye-forming coupler having a spectral absorption maximum wavelength of 500-600 nm, wavelength range 60
A cyan dye-forming coupler having a spectral absorption maximum wavelength at 0 to 750 nm is typical.

As the yellow coupler, for example, an open-chain ketomethylene coupler can be used.

Examples of the magenta coupler include, for example, 5-
A pyrazolone coupler, a pyrazolobenzimidazole coupler, a pyrazolotriazole coupler, or a closed acylacetonitrile coupler can be used.

Preferred compounds as surfactants for use in adjusting the dispersion of the photographic additive and the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfo group or a salt thereof in one molecule. Containing. Specifically, A-1 to A-11 described in JP-A-64-26854
Is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion,
It is better that the time until dispersion is added to the coating solution and the time after addition to the coating solution before coating is shorter, and it is preferably within 10 hours, more preferably within 3 hours and within 20 minutes, respectively.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds are those represented by general formulas I and II described in JP-A-2-66541, page 3.
A phenyl ether compound represented by the formula:
A phenolic compound represented by the general formula B described in JP-A-4150, an amine-based compound represented by the general formula A described in JP-A-64-90445, a general formula XII, XIII, XIV described in JP-A-62-182741; The metal complex represented by XV is particularly preferred for magenta dyes. Also, JP-A-1-1960
No. 49, a compound represented by the general formula I ';
The compounds represented by the general formula II described in JP-A-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A'-1) described in the lower left column of page 10 of the same publication are disclosed. And the like. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and the compounds described on pages 13-14 of the same publication.
Compounds 1 described on pages II-1 to II-14 and page 17 are mentioned.

For the photosensitive material, it is advantageous to use gelatin as a binder. If necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, Alternatively, a hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153.

Further, in order to prevent the growth of fungi and bacteria which adversely affect the photographic performance and the image storability, the colloid layer is disclosed in JP-A-3-15.
It is preferable to add a preservative and an antifungal agent as described in No. 7646. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

As the support used for the light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene (PE) or polyethylene terephthalate (PET), paper support made of natural pulp or synthetic pulp. body,
A vinyl chloride sheet, a polypropylene that may contain a white pigment, a PET support, baryta paper, or the like can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. PE or PET as water resistant resin
Or their copolymers are preferred.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as fine silica powder, synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, oxide Zinc, talc, clay and the like can be mentioned. Barium sulfate and titanium oxide are preferred as white pigments.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, more preferably 15% by mass, in order to improve sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support used in the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above-mentioned publication.

It is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.12 μm or less, because the effect of good gloss is obtained.
Also, in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, to adjust the spectral reflection density balance of the white background after treatment and to improve whiteness, ultramarine blue, oil-soluble dyes It is preferable to add a trace amount of a bluing agent or a reddish agent such as.

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or to an undercoat layer (adhesion, antistatic property, dimensional stability on the support surface). , One or more undercoating layers for improving friction resistance, hardness, antihalation property, frictional properties and / or other properties).

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the photosensitive material of the present invention, an image recorded on a negative may be optically formed on a photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser beam may be formed based on the digital information. May be printed by scanning while changing the intensity of the image.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display,
A light-sensitive material for color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

The light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as an alternative to the washing process, a stabilizing process may be performed. As a development processing apparatus used for the development processing of the photosensitive material, even if a roller transport type that sandwiches and transports the photosensitive material to rollers arranged in a processing tank,
An endless belt method in which the photosensitive material is fixed to the belt and conveyed may be used.However, a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is conveyed. A spray method of spraying, a wet method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. When processing in a large amount, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

[0138]

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

Example 1 High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side on which the emulsion layer was applied, a reflective polyethylene support was prepared by laminating molten polyethylene containing a surface-treated anatase type titanium oxide dispersed at a content of 15% by mass. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and a photographic component layer having the following structure was further provided to prepare Sample 101 of a silver halide photographic material.

The coating solution was prepared as follows. First layer coating liquid 3.34 g of yellow coupler (Y-1), 10.02 g of yellow coupler (Y-2), yellow coupler (Y-)
3) 1.67 g, dye image stabilizer (ST-1) 1.67
g, dye image stabilizer (ST-2) 1.67 g, dye image stabilizer (ST-5) 3.34 g, stain inhibitor (HQ)
-1) 0.167 g, image stabilizer (A) 2.67 g, image stabilizer (B) 1.34 g, high boiling organic solvent (DBP)
To 5.0 g and 1.67 g of a high boiling point organic solvent (DNP), 60 ml of ethyl acetate was added to dissolve, and a 7% aqueous gelatin solution containing 5 ml of 10% surfactant (SU-1) 32
0 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare 500 ml of a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (Em) prepared under the following conditions.
-B) to prepare a first layer coating solution.

Coating solutions for the second to seventh layers The coating solutions for the second to seventh layers were also prepared in the same manner as in the first layer.
And each coating liquid was prepared so that it might become the coating amount of Table 2.

(H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² . In the same manner as in Sample 101, Sample 102 in which the cyan coupler and the dye image stabilizer in the fifth layer were changed as shown in Table 3
To 119 were produced.

[0143]

[Table 1]

[0144]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate SU-3: di (2,2,3,3,4, sulfosuccinate) 4,
5,5, -octafluoropentyl) · sodium DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4 -Dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di- sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone Agent (A): pt-octylphenol image stabilizer ( ): Poly (t- butyl acrylamide)

[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) A monodispersed cubic emulsion EMP-1 having an average particle size of 0.71 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was prepared. . Next, a monodisperse cubic emulsion EMP-1B having an average particle size of 0.64 μm, a coefficient of variation in particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was prepared.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization using the following compounds. Similarly, EMP-1B was optimally chemically sensitized and then sensitized to EMP-1B.
1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) average particle size 0.40μ
m, a coefficient of variation of 0.08 and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5% were prepared. Next, the average particle size is 0.
50 μm, coefficient of variation 0.08, silver chloride content 99.5%
Of a monodispersed cubic emulsion EMP-2B was prepared.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization using the following compounds. Similarly, EMP-2B was also optimally chemically sensitized and then sensitized to EMP-2B.
2 and EMP-2B were mixed at a silver ratio of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion) Average particle size 0.40 μm
m, a coefficient of variation of 0.08, and a monodispersed cubic emulsion EMP-3 having a silver chloride content of 99.5% were prepared. In addition, the average particle size is 0.
38 μm, coefficient of variation 0.08, silver chloride content 99.5%
Was prepared.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization using the following compounds. Similarly, EMP-3B was optimally chemically sensitized and then sensitized to EMP-B.
3 and EMP-3B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

[0158]

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Each of the samples thus prepared was exposed to a red light wedge by a conventional method, and then subjected to a developing process in the following developing process to produce a color print having a cyan wedge image.

(Examples, processing steps) Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 30 seconds 80ml Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 120ml Stabilization 30 ~ 34 ° C. for 20 seconds 150 ml Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Pentaacetic acid pentasodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Tank solution and replenisher for bleach-fixing solution Diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water.

The above processing is referred to as processing A. Further, the above processing time is changed to the processing step processing temperature time replenishment amount Color development 38.0 ± 0.3 ° C. 18 seconds 80 ml Bleaching and fixing 35.0 ± 0.5 ° C. 19 seconds 120 ml Stabilization 30-34 ° C. 16 The processing step was changed to 150 ml / second drying 60-80 ° C. for 27 seconds as processing B.

The processing using the apparatus for processing B (application of the processing liquid from the processing liquid supply head) described in Example 1 of JP-A-11-15117 is referred to as processing C.

The processing in which the processing liquid supply head is replaced with a piezo type ink jet type array supply head for supplying the processing liquid via the gas phase is referred to as processing D.

The color reproducibility and light fastness of each processed sample were evaluated as follows. Table 3 shows the results.

<< Color Reproducibility >> The red light reflection density (D
^R _max ) was measured using a PDA-65 densitometer (manufactured by Konica Corporation), and the saturation at which a point at which the density reached 2.0 was measured with a Murakami Colorimeter was used as a measure of color reproducibility.

<< Light Resistance >> When the sample was exposed to sunlight using an underglass outdoor exposure table for two months, the red light reflection density before and after the exposure was measured with a PDA-65 (described above). The degree of fading (fading rate) due to light was determined from the following equation.

Fading rate (%) = {(D ^R _1.0 −D ^R ) / D ^R _1.0 } × 100 where D ^R _1.0 : density before light exposure (point of 1.0)
D ^R : density after light exposure Blue light reflection density (D ^B _min ) of the minimum density part of the sample is measured by PDA-65 (described above), and the degree of initial density increase by light (light stain) Was determined from the following equation.

[0171] Here light stain _{^{= (D B min -D B)}} / D B min, D B min: ( point of minimum concentration) before light exposure density D
^B : concentration after light exposure

[0172]

[Table 3]

Here, comparative coupler CC-1 is as follows.

[0174]

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Compounds 1-1 and 1-2 in Table 3 are compounds corresponding to the general formula (1) of the present invention.
Exemplified compounds 3-7 and 3 described in No. 230553
-17, and the structural formula is as follows.

[0176]

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As is clear from Table 3, the light-sensitive material containing a 2-equivalent pyrazolotriazole cyan coupler and a phenyl ether-based compound of the present invention has improved color reproducibility and without deteriorating the light stain of the dye. It can be seen that the discoloration of the dye is improved.

Example 2 A sample similar to that of Example 1 was produced. These samples were processed according to the process name CPK-2-J1 using NPS-868J manufactured by Konica Corporation as an automatic developing machine and ECOJET-P as a processing chemical.

In the same manner as in Example 1, the effect of the present invention was obtained with the sample of the present invention. Example 3 These samples were used as an automatic developing machine by using QD made by Konica Corporation.
P-1500, ECOJET-HQ as processing chemical
Using AP, processing was performed according to the process name CPK-HQA-P.

As in Example 1, the effect of the present invention was obtained with the sample of the present invention. Example 4 In the same manner as in the case of the sample 101, the same samples 402 to 419 as those of the sample 101 were prepared except that the contents described in Table 4 were changed.

Each sample was exposed to a red light wedge by a conventional method, and then developed according to the processing steps of Example 1 to produce a color print having a cyan wedge image.

The color reproducibility and light fastness of each of the processed samples were evaluated in the same manner as in Example 1. Table 4 shows the results.

[0183]

[Table 4]

Here, TCP and the comparative solvent HBS-1 are as follows. TCP: tricresyl phosphate Comparative solvent HBS-1: C ₁₇ H ₃₅ OH As is apparent from Table 4, the light-sensitive material of the present invention containing a 2-equivalent pyrazolotriazole cyan coupler and an unsaturated alcohol has a high color reproducibility. It can be seen that the dye discoloration is improved without deteriorating the light stain of the dye.
In particular, the dye image stabilizer is a phenyl ether compound represented by the general formula (1) of the present invention, and the effect is remarkable.

Example 5 Samples 502 to 520 identical to Sample 101 were prepared in the same manner as Sample 101, except that the contents shown in Table 5 were changed.

Each sample was exposed to a red light wedge by a conventional method, and then developed according to the processing steps of Example 1 to produce a color print having a cyan wedge image.

The color reproducibility and light fastness of each of the processed samples were evaluated in the same manner as in Example 1. Table 5 shows the results.

[0188]

[Table 5]

The comparative solvent HBS-2 is as follows. Comparative solvent HBS-2: CH ₃ CH ＝ CHCOOC ₁₈ H _{37 As is} apparent from Table 5, the 2-equivalent pyrazolotriazole cyan coupler of the present invention and an unsaturated bond represented by formulas (3) and (4) It can be seen that the light-sensitive material containing the compound has improved color reproducibility and improved discoloration of the dye without deteriorating the light stain of the dye. In particular, the dye image stabilizer is a phenyl ether compound represented by the general formula (1) of the present invention, and the effect is remarkable.

[0190]

The silver halide light-sensitive material of the present invention has excellent dye image fastness, image stability and color reproducibility.

Claims (7)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers contains at least one or more bi-equivalent cyan dye-forming couplers represented by the following general formulas (C-1) and (C-2), and A silver halide photographic material, wherein the silver halide emulsion layer contains a compound represented by the following general formula (1). Embedded image Wherein R ₁ represents R ₃ NH— or R ₄ O—, and R ₅ is
Represents R ₇ NH— or R ₈ O—. R ₃ , R ₄ , R ₇ and R ₈ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, and R ₂ and R ₆ each represent a substituent. X ₁
And X ₂ each represent a group capable of leaving by reaction with an oxidized form of a color developing agent. [Chemical formula 2] Wherein R ₁₁ represents an alkyl group or a trialkylsilyl group, and R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, Represents an alkenyl group, an alkenyloxy group, an acylamino group, a halogen atom, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a trialkylsilyloxy group or a sulfonamide group. Two groups out of R _{11 to} R ₁₆ are linked to form 5-6
A member ring may be formed. ] 2. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers contains at least one or more bi-equivalent cyan dye-forming couplers represented by the above general formulas (C-1) and (C-2). A silver halide photographic material, wherein the silver halide emulsion layer contains a compound represented by the following general formula (2). Formula (2) R ₂₁ -OH wherein, R ₂₁ is carbon carbon unsaturated bonds 11-3
Represents a substituent of 0. ] 3. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers contains at least one or more bi-equivalent cyan dye-forming couplers represented by the above general formulas (C-1) and (C-2). A silver halide photographic material, wherein the silver halide emulsion layer contains a compound represented by the following formula (3) or (4). General formula (3) H ₂ CＣＨCHR ₃₁ General formula (4) H ₂ C ＝ C (CH ₃ ) R ₃₂ [wherein R ₃₁ and R ₃₂ are each an alkyl group, an alkoxy group, an aryl group, an aryloxy Group, alkenyl group, alkenyloxy group, acylamino group, halogen atom, alkylthio group, arylthio group, alkoxycarbonyl group, acyloxy group, acyl group, trialkylsilyloxy group or sulfonamide group. ] 4. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers contains the compound represented by the general formula (1) and the compound represented by the general formula (2) in the same layer. material. 5. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers contains the compound represented by the general formula (1), and at least one of the compounds represented by the general formula (3) or (4) is contained in the same layer. A silver halide photographic light-sensitive material comprising: 6. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers contains at least one of the compounds represented by formula (C-1) or (C-2), and the compound represented by formula (1) is contained in the same layer.
A silver halide photographic material comprising a compound represented by the formula (1) and a compound represented by the formula (2) in the same layer. 7. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers contains at least one of the compounds represented by formula (C-1) or (C-2), and the compound represented by formula (1) is contained in the same layer.
A silver halide photographic material comprising a compound represented by the formula (1) and at least one compound represented by the formula (3) or (4) in the same layer.