JPH10123685A - Silver halide color photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic material capable of providing a sufficient coloring pigment density and having a satisfactory spectral absorptive characteristic in high density area by containing a specified coupler. SOLUTION: This photographic material contains a coupler represented by the formula I. In the formula I, Cp represents a coupler residue, L represents a divalent connecting group, J represents -CO- or -SO2 -, and R1 -R4 each represent hydrogen atom, an alkyl group or an aryl group. R5 represents a substituent, and (n) represents 0 or 1. Of the coupler residues represented by Cp, pyrazotriazoles are more preferable as the coupler residue, and a coupler represented by the formula II is particularly preferred. In the formula II, L, J, R1 -R5 , and (n) are the same as defined in the formula I, X represents hydrogen atom or a group dissociated by the reaction with an oxide body of coloring developing agent, and R represents hydrogen atom or a substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material containing a coupler having a novel ballast group.

[0002]

2. Description of the Related Art In order to add a coupler to a photographic emulsion layer in a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a color light-sensitive material, a lipophilic ballast group is introduced into a coupler molecule, It is useful to dissolve in a high boiling point organic solvent and then emulsify and disperse in a hydrophilic colloid represented by gelatin.

[0003] The basic properties required for couplers are that they have high solubility in high-boiling organic solvents and the like, that they have good dispersibility and dispersion stability in silver halide emulsions and that they do not precipitate easily, Excellent dye characteristics, excellent color tone, and clear color image in a wide color reproduction range.The obtained dye image is robust to light, heat, humidity, etc., and a simple synthesis method using inexpensive raw materials. And good reproducibility and high yield.

[0004] The role of the ballast group on these performances is significant, and is described in JP-B-44-3660 and JP-B-48-25655.
Nos. 48-25932, 48-25934, 49-16057, 51-40804, and
Nos. 7-4481, 49-8228 and 50-194
No. 35, No. 51-126831, No. 52-86333
Nos. 56-30126, 57-146251,
No. 58-42045, No. 59-177557, No. 6
No. 0-24547, U.S. Pat. Nos. 2,908,573, 2,920,961, and 3,227,544 propose specific ballast groups.

[0005] However, these ballast groups are still insufficient to satisfy the above performance.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a color dye having a sufficient density of a color dye and a spectral colorant to be formed. It is an object of the present invention to provide a color photographic material having good absorption characteristics and good spectral absorption characteristics even in a high density region.

A second object of the present invention is to provide a color photographic material containing a coupler which can be synthesized from inexpensive raw materials by a simple synthesis method with high yield and high reproducibility.

A third object of the present invention is to provide a color light-sensitive material in which a formed dye image has excellent fastness to heat, moisture and the like.

[0009]

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

(1) A silver halide color photographic light-sensitive material containing a coupler represented by the following general formula [I].

[0011]

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(Wherein Cp represents a coupler residue, L represents a divalent linking group, J represents —CO— or —SO ₂ —, and R _{1 to} R ₄ represent a hydrogen atom, an alkyl R ₅ represents a substituent, and n represents 0 or 1.) (2) The coupler represented by the general formula [I] is represented by the following general formula [II] 2. The silver halide color photographic light-sensitive material as described in 1 above,

[0013]

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[0014] _{(wherein, L, J, R 1 ~R} 5, n has the same meaning as _{L, J, R 1 ~R 5} , n in the general formula (I), X
Represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent, and R represents a hydrogen atom or a substituent. Hereinafter, the present invention will be described in detail.

In the general formula [I], Cp represents a coupler residue. Of the coupler residues represented by Cp, typical yellow coupler residues are described in US Pat.
98,443, 2,407,210, 2,87
5,057, 3,048,194, 3,44
No. 7,928 and “Falkcupler Aine Literaturwegsicht Agfa Mittileing (Band II)” @ Farkbupplereine Lite
raturbersiecht Agfa Mitt
ilung (Band II) 112-126 (196
1 year).

Of these, acylacetoanilide yellow couplers, such as benzoylacetoanilide couplers and pivaloylacetoanilide couplers, are preferred.

Representative magenta coupler residues are described in US Pat. Nos. 2,369,489 and 2,343,727.
08, 2,311,082, 2,600,78
8, 2,908,573 and 3,062,653
Nos. 3,152,896 and 3,519,429
No. 3,725,067, 4,540,654
No. JP-A-59-162548 and the aforementioned Agfa
Mittilung (Band II), pp. 126-156 (1961).

Of these, pyrazolone magenta couplers or pyrazoloazole magenta couplers (eg, pyrazoloazole magenta coupler, pyrazolotriazole magenta coupler, etc.) are preferred.

Representative cyan coupler residues are described in US Pat. Nos. 2,367,531 and 2,423,730.
No. 2,772,162, 2,895,826
Nos. 3,002,836 and 3,034,892
No. 3,041,236, JP-A-64-554 and the aforementioned Agfa Mittilung (BandI).
I) $ 156-175 (1961).

Of these, cyan couplers of phenols, cyan couplers of naphthols and cyan couplers of pyrazolotriazoles are preferred.

Among the coupler residues represented by Cp in the general formula [I], pyrazolotriazoles are more preferable as the coupler residues, and the coupler represented by the general formula [I] is preferably represented by the aforementioned general formula [II] Particularly preferred is a coupler represented by

In the general formula [I], R _{1 to} R ₄ represent a hydrogen atom, an alkyl group or an aryl group.

The alkyl group preferably has 1 to 16 carbon atoms, and may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group and the like, preferably those having 1 to 4 carbon atoms, and more preferably a methyl group.

The aryl group includes a phenyl group. The phenyl group may further have a substituent.

In the general formula [I], R _{1 to} R ₄ are particularly preferably hydrogen atoms.

In the general formula [I], J represents a —CO— group or a —SO ₂ — group, and is preferably a —CO— group.

In the general formula [I], L represents a divalent linking group, which is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl,
Cycloalkenyl, alkynyl, heterocycle, sulfonyl,
Each of sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio Derived from group 2
Represents a divalent group and a divalent group which can be formed by combining these divalent groups, preferably an alkyl, aryl, anilino, acylamino, acyloxy, sulfonamide, sulfonyl, acyl, amino group And a divalent group which can be formed by combining these divalent groups, and more preferably a divalent group derived from each of an alkyl group and an aryl group. It is a divalent group that can be formed by combining these divalent groups. n represents 0 or 1.

In the general formula [I], R ₅ represents a substituent. Examples of the substituent represented by R _5, straight-chain or branched alkyl group having 1 to 32 carbon atoms, although such as aryl groups, Other heterocyclic, and spiro compound residue, bridged hydrocarbon compound residue And the like. It is preferably an alkyl group or an aryl group having 6 to 18 carbon atoms, and these substituents may further have the same substituent as R in the general formula [II].

In the general formula [II], L, J, R _1-
R ₅ and n are L, J, R _{1 to} R ₅ and n in the general formula [I].
X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent, and R represents a hydrogen atom or a substituent.

In the general formula [II], R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups. A halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, acyloxy, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonyl, aryloxycarbonyl, Examples include heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R has 1 carbon atom.
To 32 are preferable, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

The acylamino group represented by R includes an alkylcarbonylamino group, an arylcarbonylamino group and the like.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl and aryl components of the alkylthio and arylthio groups represented by R include the alkyl and aryl groups represented by R.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 3 carbon atoms.
12, preferably 5 to 7, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

As the heterocyclic group represented by R, those having a 5- to 7-membered heterocyclic ring are preferable, and specific examples include a 2-furyl group, a 2-pyrimidinyl group and a 2-benzothiazole group.

As the sulfonyl group represented by R, an alkylsulfonyl group, an arylsulfonyl group or the like; a sulfinyl group as an alkylsulfinyl group, an arylsulfinyl group, or the like; a phosphonyl group as an alkylphosphonyl group, an arylphosphonyl group, or the like; Groups include alkylcarbonyl groups and arylcarbonyl groups; carbamoyl groups include alkylcarbamoyl groups and arylcarbamoyl groups; sulfamoyl groups include alkylsulfamoyl groups and arylsulfamoyl groups; acyloxy groups include alkylcarbonyloxy groups Imide groups such as succinimide group, 3-heptadecylsuccinimide group, phthalimide group and glutarimide group; ureido groups such as alkylureido group and aryl Ruureido group or the like; examples of the heterocyclic thio group is preferably a heterocyclic thio group 5- to 7-membered, particularly 2-pyridylthio group, 2-benzothiazolylthio group or the like;
As the spiro compound residue, spiro [3.3] heptane-
1-yl and the like; bridged hydrocarbon compound residues include bicyclo [2.2.1] heptane-1-yl and tricyclo [1.
3.13.17] decane-1-yl, 7,7-dimethyl-biticlo [2.2.1] heptan-1-yl and the like.

These groups may be further substituted by the above substituents. Among these, for example, alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, acyloxy, alkylamino, imide, Each group such as alkoxycarbonyl, aryloxycarbonyl, ureido and the like is preferable, and an alkyl group is more preferable, and a methyl group is particularly preferable.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkylene, an alkoxy, an aryloxy, a heterocyclic oxy, an acyloxy ,
Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl and the like, but preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, It is a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a nitrogen-containing composite ring bonded by an N atom. More preferably, it is a halogen atom, especially a chlorine atom.

Next, typical examples of the compound represented by the general formula [I] of the present invention are shown below, but the present invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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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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The following is a synthesis example of a typical compound represented by the general formula [I] of the present invention.

(Synthesis Example) The exemplified compound (M-15) was synthesized according to the following scheme.

[0056]

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I) Synthesis of Intermediate 1 9.85 g of the compound described in JP-A-60-55343 and 11.1 g of acrylic acid were prepared by adding isopropyl alcohol (IPA)
Dissolve in 100 ml and heat to reflux for 6 hours. After completion of the reaction, the mixture was cooled and recrystallized to obtain 10.3 of Intermediate 1.
g was obtained. The identification was performed by MASS, H-NMR, and IR spectrum, and it was confirmed that it was Intermediate 1.

II) Synthesis of Intermediate 2 9.45 g of Intermediate 1 was dissolved in 35 ml of a mixed solvent of DMF: THF = 2: 5, cooled to 5 ° C., and N-chloro-succinimide was maintained at this temperature. (NCS)
4.26 g are added slowly. After stirring for 1 hour after the addition, 100 ml of water was added for precipitation.
2 g were obtained. The identification was performed by MASS, H-NMR, and IR spectrum, and it was confirmed that it was Intermediate 2.

III) Synthesis of Exemplified Compound (M-15) 5.0 g of Intermediate 2 was dissolved in 75 ml of ethyl acetate, 75 ml of water and 1.7 g of sodium acetate were added, and the mixture was cooled to 10 ° C. 00 g is slowly added dropwise over 15 minutes. After completion of the dropping, the temperature is returned to room temperature with stirring.
Stir for hours. After extraction with ethyl acetate, neutralization, washing with water, drying, the solvent was removed under reduced pressure, and the obtained crude crystals were recrystallized from ethyl acetate and acetonitrile mixed solvent 25 ml,
7.22 g of exemplified compound (M-15) was obtained. Identification is M
ASS, H-NMR and IR spectra confirmed that it was Exemplified Compound (M-15).

Other couplers of the present invention can be synthesized according to the above.

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

The coupler of the present invention can be used in combination with other types of couplers.

As the coupler of the present invention, typically, a method of blending the coupler of the present invention with a silver halide emulsion and coating the emulsion on a support to form a color photographic material is preferably used.

The coupler of the present invention is used for color photographic light-sensitive materials such as negative and positive films of the coupler and color printing paper.

The light-sensitive material using the coupler of the present invention such as the color photographic paper may be of a single color or a multicolor. In the multicolor photosensitive material, the coupler of the present invention may be contained in any layer. The multicolor light-sensitive material has a dye image-forming constituent unit having photosensitivity in each of three primary color regions of the spectrum. Each structural unit can be composed of a single layer or multiple emulsion layers sensitive to a certain region of the spectrum. The constituent layers of the light-sensitive material, including the layers of the image forming constituent units, can be arranged in various orders as known in the art.

A typical multicolor photosensitive material has at least one photosensitive material.
Cyan dye image forming unit comprising at least one red-sensitive silver halide emulsion layer containing two cyan couplers, magenta dye image comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler A yellow dye image forming structural unit comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler is supported on a support.

The light-sensitive material can have additional layers such as a filter layer, an intermediate layer, a protective layer, an undercoat layer or an undercoat layer.

For incorporating the coupler of the present invention into an emulsion, a conventionally known method may be used. For example, the boiling point of tricresyl phosphate, dibutyl phthalate, etc. is 175 ° C.
After dissolving the coupler of the present invention alone or in combination with a high-boiling organic solvent or a low-boiling solvent such as butyl acetate or butyl propionate alone or, if necessary, a mixture thereof, a surfactant is added. After mixing with a gelatin aqueous solution containing the mixture and emulsifying the mixture with a high-speed rotation mixer or a colloid mill, the mixture is added to silver halide to prepare a silver halide emulsion used in the present invention.

The silver halide composition preferably used for the light-sensitive material using the coupler of the present invention includes silver chloride, silver chlorobromide or silver chloroiodobromide. Further, a combination mixture such as a mixture of silver chloride and silver bromide may be used. That is, when a silver halide emulsion is used for color photographic paper, particularly fast developability is required. Therefore, the silver halide preferably contains a chlorine atom as a halogen composition, and is preferably silver chloride or at least 1 mol%. Particularly preferred is silver chlorobromide or silver chloroiodobromide containing silver chloride.

The silver halide emulsion is chemically sensitized by a conventional method. Further, it can be optically sensitized to a desired wavelength range.

The silver halide emulsion is used to prevent fogging during the production process, storage, or photographic processing of the light-sensitive material, and / or
Alternatively, a compound known as an antifoggant or stabilizer in the photographic industry for the purpose of keeping photographic performance stable can be added.

The color light-sensitive material using the coupler of the present invention includes a color antifoggant, a dye image stabilizer, an ultraviolet light inhibitor, an antistatic agent, a matting agent, which are usually used in light-sensitive materials.
Various additives such as a surfactant can be used.

These are described, for example, in Research Disclosure (Research Disclosure).
e) The description in volume 176, pages 22 to 31 (December 1978) can be referred to.

The color photographic light-sensitive material using the coupler of the present invention can form an image by performing a color development process known in the art.

The color photographic light-sensitive material using the coupler of the present invention contains a color developing agent in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof, and can be processed by an alkaline activating bath. .

The color photographic light-sensitive material using the coupler 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, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[0078]

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 The following layers were sequentially coated on a paper support laminated on both sides with polyethylene from the support side to prepare a green photosensitive color photosensitive material sample 1. The amount of the compound added is shown per 1 m ² unless otherwise specified (silver halide is a silver equivalent value).

First layer: emulsion layer 1.4 g of gelatin, green-sensitive silver chlorobromide emulsion (silver chloride 99.
7.5 × 10 ^{-4 of} Comparative coupler 1 dissolved in 0.17 mol of 0.15 mol and 0.26 g of dioctyl phthalate
Green sensitive emulsion layer consisting of moles.

Second layer: protective layer A protective layer containing 0.50 g of gelatin. In addition, sodium salt of 2,4-dichloro-6-hydroxy-s-triazine was added as a hardening agent in an amount of 0.017 g per 1 g of gelatin.

Next, Sample 2 of the present invention was prepared in exactly the same manner as in Sample 1 except that Comparative Coupler 1 was replaced with a coupler shown in Table 1 (the amount added was the same molar amount as Comparative Coupler 1).
To 8 were prepared.

[0083]

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Each of the samples thus prepared was subjected to wedge exposure with green light according to a conventional method, and then processed according to the following processing steps.

Processing temperature
Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds The composition of each processing solution is as follows. Shown in The replenishment amount of each processing solution is 80 cc per m ^{2 of the} color photographic light-sensitive material.

Color developing solution Tank solution Replenisher Pure water 800 cc 800 cc Triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g -1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1. 8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g 8.2 g Fluorescent brightener (4,4′-diaminostilbene disulfonic acid derivative) 1.0 g 1 8.8 g Potassium carbonate 27 g 27 g Water was added to make the total volume 1000 cc. The pH of the tank solution was 10.10, and the pH of the replenisher was 10.
Adjust to 60.

Bleaching / fixing solution (tank solution and replenisher are the same) Ferric ammonium ammonium diaminetetraacetate 60 g ethylenediaminetetraacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 cc ammonium sulfite (40% aqueous solution) 27.5 cc water In addition, the total amount is adjusted to 1000 cc, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (the tank solution and the replenishing solution are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Water is added to make the total amount 1000 cc, and sulfuric acid or water Adjust the pH to 7.0 with potassium oxide.

The maximum density (Dmax) of each of the processed samples 1 to 8 was measured using a densitometer (model KD-7, manufactured by Konica Corporation). Measure the spectral reflection spectrum where
The maximum absorption wavelength (λmax) and Δλ _L 0.2 were determined.
Δλ _L 0.2 normalizes the absorbance at λmax to 1, and the wavelength at which the absorbance becomes 0.2 on the longer wavelength side than λmax is λ.
_{When L is} 0.2, the value is represented by λ _L 0.2−λmax.

[0090]

[Table 1]

As is evident from the results in Table 1, the samples using the coupler of the present invention have higher Dmax and better color development than the samples using the comparative coupler 2, and the long-wave-side edge (Δλ _L) 0.2), which is good, indicating that the sample of the present invention has an excellent effect.

Example 2 Polyethylene was laminated on one side of a paper support, and polyethylene having titanium oxide was laminated on the other side. On the support, each layer having the following constitution was replaced with a polyethylene layer containing titanium oxide. To prepare Sample 9 of a multilayer silver halide color photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (EY-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (S
T-2) 6.67 g, additive (HQ-1) 0.67 g,
60 ml of ethyl acetate was added to 6.67 g of the anti-irradiation dye (AI-3) and the high boiling point organic solvent (DNP) to dissolve the solution, and this solution was dissolved in 7 ml of a 20% surfactant (SU-1).
Was dispersed and emulsified in 220 ml of a 10% aqueous gelatin solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were also prepared in the same manner as the coating liquid for the first layer.

As a hardening agent, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The amount added in the silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 4
The following (solution A) and (solution B) were pAg = 6.5 and pH = 3 in 1000 ml of a 2% aqueous gelatin solution kept at 0 ° C.
0 and added simultaneously over 30 minutes.
Solution) and (D Solution) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.
For control of pAg, a control solution having the following composition was used. The composition of the control liquid is a mixed halide salt aqueous solution composed of sodium chloride and potassium sulfide, the ratio of chloride ions to bromide ions is 99.8: 0.2, and the concentration of the control liquid is
When mixing (Solution A) and (Solution B), 0.1 mol / L is used, and when mixing (Solution C) and (Solution D), 1 mol / L is used.
Liters.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide Water was added to make up to 200 ml.

(Solution B) 10 g of silver nitrate was added to make up to 200 ml.

(Solution C) 102.7 g of sodium chloride 1.0 g of potassium bromide Water was added to make up to 600 ml.

(Solution D) Silver nitrate (300 g) was added to water to make up to 600 ml.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
a Desalting was performed using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle diameter of 0.85 μm, a variation coefficient of 0.07, and a silver chloride content of 99.5 mol. % Of a monodispersed cubic emulsion EMP-1.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds 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 6 × 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 (Preparation method for green-sensitive silver halide emulsion) Addition time of (Solution A) and (Solution B) and the time of (Solution C) and (Solution D) Except for changing the addition time, in the same manner as in EMP-1, the average particle size is 0.43 μm, the variation coefficient is 0.08, and the silver chloride content is 99.
A 5 mol% monodisperse cubic emulsion EMP-2 was obtained.

The following compound was used for EMP-2.
Chemical ripening was performed at 5 ° C. for 120 minutes 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 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation method of red-sensitive silver halide emulsion) (Solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodispersed cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

EMP-3 was prepared by using the following compound.
Chemical ripening was performed at 0 ° C. for 90 minutes 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 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX The coefficient of variation was a value obtained by dividing the standard deviation by the average particle size, and was calculated from 100 electron micrographs of silver halide grains.

[0117]

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Next, in the same manner as in Sample 9, except that the comparative coupler 1 (EM-1) in the third layer was replaced with the coupler shown in Table 4 (the amount of addition was the same as that of the comparative coupler 1). Samples 10 to 20 were produced.

The obtained sample was exposed to wedges in the same manner as in Example 1 and then developed to obtain a green-sensitive layer having Dmax and λma.
x and Δλ _L 0.2 were measured. The results are summarized in Table 4.

[0120]

[Table 4]

As is evident from the results in Table 4, the samples using the coupler of the present invention have higher Dmax and better coloring properties than the samples using the comparative couplers 1 and 2, and have a Δλ _L 0. 2 is small and also excellent in color reproducibility.

Example 3 Samples 21 to 24 were prepared in exactly the same manner as in Example 2 except that the coupler (EM-1) in the third layer was replaced with the coupler shown in Table 5 (the amount added was the same molar amount). Produced.

The obtained sample was exposed to wedges in the same manner as in Example 1, developed, and the (Dmax) of the green-sensitive layer was measured.

Further, a color checker (manufactured by Macbeth)
Was photographed with Konica Color DD100 (manufactured by Konica Corporation), and a negative film obtained by development was adjusted to the color tone of the gray portion, and then printed on the sample prepared above, color-developed and color reproducibility was evaluated.

Table 5 summarizes the results.

[0126]

[Table 5]

[0127]

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From the results shown in Table 5, it can be seen that all of the samples of the present invention using the coupler of the present invention have a higher maximum color density and are superior in color reproducibility as compared with the comparative sample.

Example 4 Samples were prepared in exactly the same manner as in Example 2 except that the couplers (EC-1, EC-2) in the fifth layer were replaced with the couplers shown in Table 6 (addition amounts were the same molar amounts). 25-28 were produced.

The obtained sample was exposed to wedges in the same manner as in Example 1, developed, and the Dmax of the red-sensitive layer was measured.

Further, a color checker (manufactured by Macbeth)
Was photographed with Konica Color DD100 (manufactured by Konica Corporation), and a negative film obtained by development was adjusted to the color tone of the gray portion, and then printed on the sample prepared above, color-developed and color reproducibility was evaluated.

Table 6 summarizes the results.

[0133]

[Table 6]

[0134]

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From the results shown in Table 6, it can be seen that all of the samples of the present invention using the coupler of the present invention have higher maximum color density and excellent color reproducibility than the comparative sample.

Example 5 Samples 30 to 33 were prepared in exactly the same manner as in Example 2 except that the coupler (EY-1) in the first layer was replaced with the coupler shown in Table 7 (addition amount was the same molar amount). Produced.

The obtained sample was exposed to wedges in the same manner as in Example 1, developed, and the Dmax of the blue-sensitive layer was measured.

Furthermore, a color checker (manufactured by Macbeth)
Was photographed with Konica Color DD100 (manufactured by Konica Corporation), and a negative film obtained by development was adjusted to the color tone of the gray portion, and then printed on the sample prepared above, color-developed and color reproducibility was evaluated.

[0139]

[Table 7]

[0140]

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From the results shown in Table 7, it can be seen that all of the samples of the present invention using the coupler of the present invention have a higher maximum density than the comparative sample and are excellent in color reproducibility.

[0142]

According to the present invention, a silver halide color photographic light-sensitive material having a sufficient color-dye density, excellent spectral absorption characteristics of the formed color-dye, and excellent spectral absorption characteristics even in a high density range. I got the ingredients. In addition, a coupler having high yield and good reproducibility can be obtained from inexpensive raw materials by a simple synthesis method.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ryohei Iwamoto 1st Konica Corporation, Sakura-cho, Hino-shi, Tokyo In-house (72) Inventor Satoru 1st Konica Corporation, Sakura-cho, Hino-shi, Tokyo In-house

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material containing a coupler represented by the following general formula [I]. Embedded image (Wherein, Cp represents a coupler residue, L represents a divalent linking group, J represents —CO— or —SO ₂ —, and R _{1 to} R ₄
Represents a hydrogen atom, an alkyl group or an aryl group, respectively. R ₅ represents a substituent, and n represents 0 or 1. ) 2. The method according to claim 1, wherein the coupler represented by the general formula [I] is represented by the following general formula [II].
The silver halide color photographic light-sensitive material described in the above. Embedded image _{(Wherein, L, J, R 1 ~R} 5, n has the same meaning as _{L, J, R 1 ~R 5} , n in the general formula (I), X is an oxidation of the hydrogen atom or a color developing agent And R represents a hydrogen atom or a substituent.)