JPH0619083A - Silver halide color photographing sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material containing a two-equiv. yellow coupler which can be produced at low cost, has excellent color developing property, color reproducibility, and image preservation property, high solubility in solvents of low and high boiling point, and excellent dispersion stability. CONSTITUTION:This silver halide color photographic sensitive material has at least one silver halide emulsion layer on a supporting body, and at least one silver halide emulsion layer contains a two-equiv. yellow coupler expressed by formula. In formula, R1 and R2 are hydrogen atoms, alkyl groups, cycloalkyl groups, or aryl groups, R3 is an alkyl group, cycloalkyl group, or aryl group, R4 is a substituent, R5 and R6 are hydrogen atoms, alkyl groups, cycloalkyl groups, or aryl groups, and (n) is an integer 0-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, it can be manufactured at low cost, has excellent color developability and color reproducibility, is excellent in image storability, and is capable of dispersing a coupler. The present invention relates to a silver halide color photographic light-sensitive material containing a novel 2-equivalent yellow coupler having high solubility in low-boiling and high-boiling solvents used and having excellent dispersion stability in a silver halide emulsion layer.

[0002]

BACKGROUND OF THE INVENTION Recently, in silver halide color photographic light-sensitive materials (hereinafter also simply referred to as color light-sensitive materials),
Instead of the traditional 4-equivalent coupler, which required 4 atoms of silver to form the dye of the molecule, introduce a suitable substituent at the coupling position (active site) of the coupler that reacts with the oxide of the developing agent. As a result, a 2-equivalent coupler in which two atoms of silver are sufficient to form one molecule of dye tends to be used.

[0003]

However, the demands on couplers have become more and more stringent with the progress of color light-sensitive materials, and not only color development but also color reproducibility, image storability, solubility in low boiling point solvents, and Further improvements in dispersion stability are required.

As an example of a yellow coupler satisfying good color reproducibility and high color development and further improving light resistance,
For example, a yellow coupler having an alkoxy group at the 2-position and an acylamino group at the 5-position of the anilide portion as described in JP-A-63-123047 can be mentioned. However, these couplers have essentially high pKa values and are not completely satisfactory in terms of color development. Further, since these couplers have poor solubility in low-boiling point solvents such as ethyl acetate and high-boiling point solvents such as dibutyl phthalate, a large amount of solvent must be used for dispersion, which is an inconvenience in the production of color photosensitive materials. Further, it has a drawback that it is liable to be generated and, after being once dispersed in the solvent, is likely to cause precipitation. Under the conditions for thinning, which have been strongly aimed in recent years, these drawbacks are remarkably emphasized, and it has become clear that they pose a serious obstacle to practical use.

US Pat. No. 5,118,599 describes a new yellow coupler having a dioxane cyclic structure in the molecule. These couplers have an advantage of being excellent in solubility in an organic solvent and dispersion stability in the solvent, but they are not at a completely satisfactory level in terms of color forming property. Further, it has been revealed that it also has a drawback that it is slightly inferior to the conventional couplers in terms of light resistance.

The present invention has been made in view of the above problems, and the first object of the present invention is to manufacture it at low cost.
It is an object of the present invention to provide a silver halide color photographic light-sensitive material containing a novel 2-equivalent yellow coupler excellent in color forming property.

A second object of the present invention is to provide a novel 2-equivalent yellow coupler which has a high solubility in low-boiling and high-boiling solvents used to disperse the coupler and exhibits excellent dispersion stability in the solvent. A silver halide color photographic light-sensitive material containing the same is provided.

A third object of the present invention is to react with an oxidant of a developing agent during color development to provide excellent image storability (especially excellent light fastness) and faithful color reproducibility. It is to provide a silver halide color photographic light-sensitive material containing a novel 2-equivalent yellow coupler capable of forming a dye showing a sharp visible absorption spectrum and giving a bright color image.

[0009]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and at least one of the silver halide emulsion layers. And a 2-equivalent yellow coupler represented by the following general formula [I] are contained in the silver halide color photographic light-sensitive material.

[0010]

[Chemical 2] [Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
Represents a cycloalkyl group and an aryl group, R ₃ represents an alkyl group, a cycloalkyl group or an aryl group,
R ₄ represents a substituent, and R ₅ and R ₆ represent a hydrogen atom, an alkyl group, a cycloalkyl group and an aryl group, respectively. n represents an integer from 0 to 4. ]

In the above general formula [I], R ₁ and R
₂ is a hydrogen atom, a linear or branched alkyl group (eg, methyl group, ethyl group, i-propyl group, n-
Propyl group, t-butyl group, n-butyl group, 1-hexylnonyl group, etc.), cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, bicyclo [2.2.1] heptyl group, adamantyl group, etc.), and It represents an aryl group (for example, a phenyl group, a 1-naphthyl group, a 9-anthranyl group, etc.). The alkyl group, cycloalkyl group, and aryl group represented by R ₁ or R ₂ may further have a substituent, and examples of the substituent include an alkyl group represented by R ₁ or R ₂ , a cycloalkyl group, and In addition to a group having the same meaning as an aryl group, a halogen atom-substituted alkyl group (eg, trifluoromethyl group), a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group,
Nitro group, alkenyl group (eg 2-propylene group, oleyl group etc.), hydroxy group, alkoxy group (eg methoxy group, 2-ethoxyethoxy group etc.), aryloxy group (eg phenoxy group, 2,4-di-t). -Amylphenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group etc.), heterocyclic oxy group (eg 4-pyridyloxy group, 2-hexahydropyranyloxy group etc.), carbonyloxy group (eg acetyloxy group) ,
Trifluoroacetyloxy group, alkylcarbonyloxy group such as pivaloyloxy group, benzoyloxy group,
Aryloxy group such as pentafluorobenzoyloxy group), sulfonyloxy group (for example, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, n
An alkylsulfonyloxy group such as a dodecanesulfonyloxy group, a benzenesulfonyloxy group, an arylsulfonyloxy group such as a p-toluenesulfonyloxy group), a carbonyl group (for example, an acetyl group, an alkylcarbonyl group such as a trifluoroacetylpivaloyl group) , Benzoyl group, pentafluorobenzoyl group, 3,5-di-
an arylcarbonyl group such as t-butyl-4-hydroxybenzoyl group), an oxycarbonyl group (for example, a methoxycarbonyl group, a cyclohexyloxycarbonyl group,
Alkoxycarbonyl group such as n-dodecyloxycarbonyl group, phenoxycarbonyl group, 2,4-di-t-amylphenoxycarbonyl group, aryloxycarbonyl group such as 1-naphthyloxycarbonyl group, and 2-
Heterocyclic oxycarbonyl groups such as pyridyloxycarbonyl group and 1-phenylpyrazolyl-5-oxycarbonyl group), carbamoyl groups (eg dimethylcarbamoyl group, 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl) Groups such as alkylcarbamoyl groups, phenylcarbamoyl groups, 1-naphthylcarbamoyl groups and other arylcarbamoyl groups), sulfonyl groups (eg, methanesulfonyl groups, trifluoromethanesulfonyl groups, and other alkylsulfonyl groups, and p-toluenesulfonyl groups, and other aryl groups) Sulfonyl group), sulfamoyl group (eg, dimethylsulfamoyl group, 4- (2,4-di-t-amylphenoxy) butylaminosulfonyl group and other alkylsulfamoyl groups, phenylsulfamoyl group and other arylsulfamoyl groups) Amoiru group), an amino group (e.g., dimethylamino group, cyclohexylamino group, an alkylamino group such as n- dodecyl amino group, an anilino group, p-
an arylamino group such as t-octylanilino group), a sulfonylamino group (for example, a methanesulfonylamino group,
Heptafluoropropanesulfonylamino group, alkylsulfonylamino group such as n-hexadecylsulfonylamino group, p-toluenesulfonyl group, arylsulfonylamino group such as pentafluorobenzenesulfonylamino), acylamino group (eg, acetylamino group, myristoylamino group) Groups such as alkylcarbonylamino groups, benzoylamino groups such as arylcarbonylamino groups), alkylthio groups (eg, methylthio groups, t-octylthio groups, etc.), arylthio groups (eg, phenylthio groups, etc.),
And a heterocyclic thio group (for example, 1-phenyltetrazole-5-thio group, 5-methyl-1,3,4-oxadiazole-2-thio group, etc.) and the like.

R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In the above general formula [I], R ₃ represents a group having the same meaning as the alkyl group, cycloalkyl group and aryl group represented by R ₁ or R ₂ in the above general formula [I]. Further, the alkyl group, cycloalkyl group and aryl group represented by R ₃ may have a substituent, and examples of the substituent include the alkyl group represented by R ₁ or R ₂ in the general formula [I]. , A cycloalkyl group, and a group having the same meaning as the group described as the substituent of the aryl group.

R ₃ preferably has 1 to 20 carbon atoms.
Up to an alkyl group or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In the above general formula [I], R ₄ represents a substitutable substituent on the benzene ring, for example, an alkyl group represented by R ₁ or R ₂ in the above general formula [I],
Examples thereof include a group having the same meaning as the group described as the substituent of the cycloalkyl group and the aryl group.

In the above general formula [I], n represents an integer from 0 to 4, and when n is 2 or more, R ₄ may be the same or different substituents. In that case, a plurality of R _{4 s} may be bonded to each other to form a ring structure.

In the above general formula [I], R ₅ and R ₆ are each a hydrogen atom or an alkyl group, a cycloalkyl group represented by R ₁ or R ₂ in the above general formula [I],
And a group having the same meaning as the aryl group. The alkyl group, cycloalkyl group, and aryl group represented by R ₅ or R ₆ may have a substituent, and examples of the substituent include R ₁ or R ₂ in the above general formula [I].
Examples of the substituent are the same as those described as the substituents of the alkyl group, cycloalkyl group, and aryl group represented by.

R ₅ and R ₆ are each 1 to 20 carbon atoms.
Up to an alkyl group and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

The two-equivalent yellow coupler represented by the above general formula [I] may be bonded at any substituent to form a bis-form, tris-form, tetrakis-form or polymer form.

Typical examples of the two-equivalent yellow coupler represented by the general formula [I] (hereinafter sometimes referred to as "yellow coupler of the present invention") used in the present invention are shown below. Is not limited by.

[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

[0032]

[Chemical 14]

[0033]

[Chemical 15]

[0034]

[Chemical 16]

[0035]

[Chemical 17]

[0036]

[Chemical 18]

[0037]

[Chemical 19]

[0038]

[Chemical 20]

[0039]

[Chemical 21]

The yellow coupler of the present invention can be easily synthesized by a conventionally known method. A typical synthesis example is shown below.

[0041]

[Chemical formula 22] 12.8 g of 4-equivalent coupler (A) was dissolved in 100 ml of chloroform, and 2.8 g of sulfuryl chloride was added dropwise under ice cooling. After dropping
The reaction solution was washed with water and dehydrated with magnesium sulfate, and the solvent was removed under reduced pressure.

The obtained residue was dissolved in 100 ml of acetone, 5.6 g of compound (B) and 2.9 g of potassium carbonate were added, and the mixture was heated under reflux for 2 hours. The insoluble material was filtered off and washed with 5% aqueous potassium carbonate solution and diluted hydrochloric acid. After dehydration with magnesium sulfate, the solvent was removed under reduced pressure, and the residue was replaced with 70 ml of i
-Recrystallization from propanol gave the desired exemplary coupler (1). The yield was 7.5 g (43%). 4
The equivalent coupler (A) was synthesized according to the method described in US Pat. No. 5,118,599.

The structure of the exemplified coupler (1) has NMR, I
It was confirmed by R and mass spectrum. Exemplified couplers other than Exemplified coupler (1) were also synthesized according to the above-mentioned synthesis examples, starting from the corresponding raw materials.

The yellow coupler of the present invention may be one type or two types.
A combination of two or more species can be used. It can also be used in combination with any known pivaloylacetanilide or benzoylacetanilide yellow coupler.

To incorporate the yellow coupler of the present invention into a silver halide photographic emulsion of a color photographic light-sensitive material, for example, a high boiling point organic solvent having a boiling point of 175 ° C. or higher such as tricresyl phosphate or dibutyl phthalate and ethyl acetate, One of the low boiling organic solvents conventionally used in preparing coupler dispersions, such as methanol, acetone, chloroform, methyl chloride or butyl propionate.
After dissolving in one or two or more kinds alone or in combination, it is mixed with an aqueous gelatin solution containing a surfactant, and then the mixture is emulsified and dispersed by a high speed rotary mixer or a colloid mill, and then the obtained emulsification The dispersion is added directly to the silver halide photographic emulsion, or the above emulsion dispersion is set, then shredded, and then the low boiling point organic solvent is removed by a means such as washing with water. It may be added to the photographic emulsion.

Generally, the yellow coupler of the present invention is preferably added in an amount of about 1 × 10 ^-3 mol to about 1 mol per mol of silver halide, but the amount added may vary depending on the purpose of application. You may.

The silver halide color photographic light-sensitive material of the present invention may be of any kind and use, and
As the silver halide, for example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. are used.

The silver halide color photographic light-sensitive material of the present invention may contain other color couplers for forming a multicolor image in addition to the yellow coupler of the present invention.

In the silver halide color photographic light-sensitive material of the present invention, a color antifoggant, an image stabilizer, a hardener, a plasticizer, a polymer latex, a formalin scavenger, a mordant, a development accelerator, a development retarder, and a fluorescence enhancer. A whitening agent, a matting agent, a solvent, an antistatic agent, a surfactant and the like can be optionally used.

By incorporating an ultraviolet absorber into the silver halide color photographic light-sensitive material containing the yellow coupler of the present invention, the durability of the yellow image produced on the light-sensitive material can be further improved.

[0051]

EXAMPLES Next, the present invention will be described with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 On a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side, each layer having the following constitution was formed into a polyethylene layer containing titanium oxide. A multilayer silver halide color photographic light-sensitive material sample 101 was prepared by coating on the side. However, the coating solution was prepared as follows.

First layer coating liquid 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2) 6.6
To 7 g, 0.67 g of additive (HQ-1), anti-irradiation dye (AI-3) and 6.67 g of high boiling organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution was dissolved in 20% surfactant (SU). -1) 10% gelatin aqueous solution containing 7 ml 22
Emulsified and dispersed in 0 ml 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 coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardener, the second and fourth layers (H
-1) and (H-2) were added to the 7th layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Chemical formula 23]

[0059]

[Chemical formula 24]

[0060]

[Chemical 25]

[0061]

[Chemical formula 26]

[0062]

[Chemical 27]

[0063]

[Chemical 28]

[0064]

[Chemical 29]

(Method for preparing blue-sensitive silver halide emulsion) 40
In 1000 ml of 2% gelatin aqueous solution kept at ℃, the following (A
Liquid 3) and (B liquid) are controlled to pH = 6.5 and pH = 3.0.
Simultaneously added over 0 minutes, and further (C solution) and (D
(Solution) was simultaneously added over 180 minutes while controlling pH = 7.3 and pH = 5.5. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. A control solution was used to control pAg. As the control liquid, a mixed halide salt aqueous solution containing sodium chloride and potassium bromide having a chloride ion / bromide ion ratio of 99.8: 0.2 was used. The concentration of the control liquid was 0.1 mol / liter when mixing the liquids A and B, and 1 mol / liter when mixing the liquids C and D.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make up to 200 ml. (Solution B) 10 g of silver nitrate was added to make 200 ml. (Liquid C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make up to 600 ml. (Solution D) 300 g of silver nitrate was added to make 600 ml.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B). However, the amounts of the following compounds used are shown per mol of silver halide. Sodium thiosulfate 0.8 mg Chloroauric acid 0.5 mg Stabilizer STAB-1 6 × 10 ^-4 mol Sensitizing dye BS-1 4 × 10 ^-4 mol Sensitizing dye BS-2 1 × 10 ^-4 mol

[0069]

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G). However, the amounts of the following compounds used are shown per mol of silver halide. Sodium thiosulfate 1.5 mg Chloroauric acid 1.0 mg Stabilizer STAB-1 6 × 10 ^-4 mol Sensitizing dye GS-1 4 × 10 ^-4 mol

[0071]

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R) was obtained. However, the amounts of the following compounds used are shown per mol of silver halide. Sodium thiosulfate 1.8 mg Chloroauric acid 2.0 mg Stabilizer STAB-1 6 × 10 ^-4 mol Sensitizing dye RS-1 1 × 10 ^-4 mol

[0073]

[0074]

[Equation 1] (Ri represents the particle size, and ni represents the number of particles having the particle size ri.)

[0075]

[Chemical 30]

[0076]

[Chemical 31]

Then, Samples 102 to 115 were prepared in the same manner as Sample 101 except that the yellow coupler of the first layer was changed as shown in Table 3 in the preparation of Sample 101. The addition amount of the yellow coupler was adjusted to be the same as the addition amount of Sample 101.

The prepared sample was wedge-exposed to white light for 0.2 seconds, color-developed according to the following processing steps, and then the maximum color density Dmax and the minimum density Dmin were measured with an optical densitometer (PDA-65 type manufactured by Konica). It was measured.

The above sample was exposed to sunlight for 4 weeks,
The residual concentration at the initial concentration of 1.0 was measured.

The results are shown in Table 3.

The processing conditions are as follows. Processing process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds

Color developing solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine Tetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener ( 4,4'-Diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to make 1 liter, Adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g o-Phenylphenol sodium 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter. And adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

[0085]

[Table 3] From the results shown in Table 3, all of the samples using the coupler of the present invention showed high light-fastness as well as formation of image dyes having a higher maximum color density and less fog than the comparative samples. You can see that

Example 2 One Side (Surface) of Triacetyl Cellulose Film Support
Was subjected to an undercoating treatment, and then the support was sandwiched between the support and a surface opposite to the surface subjected to the undercoating treatment (rear surface) to sequentially form a layer having the following composition from the support side.

A multilayer color photographic light-sensitive material sample 201 was prepared by sequentially forming each layer having the composition shown below from the side of the support on the surface of the triacetyl cellulose film support subjected to the undercoating process. The addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified.

First layer; antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Compound (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent ( Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm) 0.4 g (average iodine content 2.0 mol%) Silver iodobromide emulsion (average grain size 0.4 μm) 0.3 g (average iodine content 8.0 mol%) Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ (mol / Silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1) ) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm) 0.9 g (average iodine content 7.5 mol) %) Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) 0.6 g (containing average iodine) Amount 8.0 mol%) Silver iodobromide emulsion (average grain size 0.3 μm) 0.2 g (average iodine content 2.0 mol%) Sensitizing dye (S-4) 6.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitization Dye (S- ) 0.8 × 10 ^-4 (mol / mole of silver) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm) 0.9 g (average iodine content 7.5 mol% ) Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point Solvent (Oil-2) 0.35 g Gelatin 1.0 g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive ( S-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g 9th layer; low-sensitivity blue-sensitive emulsion layer (B- L) Silver iodobromide emulsion (average grain size 0.3 μm) 0.25 g (average iodine content 2.0 mol%) Silver iodobromide emulsion (average grain size 0.4 μm) 0.25 g (average iodine content 8.0 mol%) Sensitization Dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1a) 0.6 g Yellow coupler (Y-1b) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D- 2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm) 0.5 g (containing average iodine) The amount 8.5 mol%) sensitizing dye (S-10) 3 × 10 -4 ( mol / mole of silver) sensitizing dye (S-11) 1.2 × 10 -4 ( mol / mole of silver) yellow coupler Y-1a) 0.18 g Yellow coupler (Y-1b) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling solvent (Oil-1) 0.07 g High boiling point solvent (Oil-3) 0.07 g Gelatin 0.8 g 12th layer; Second protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate : Ethyl methacrylate: Methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size 3 μm) 0.13 g

The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains (silver iodide content 2 mol%) having an average grain size of 0.33 μm as seed crystals.

The solution <G-1> was heated to a temperature of 70 ° C., pH of 7.8 and pH of 7.8.
The seed emulsion corresponding to 0.34 mol was added while maintaining the ratio at 7.0 while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, while maintaining a flow rate ratio of <H-1> and <S-1> of 1: 1, the accelerated flow rate (the flow rate at the end is Initial flow rate of 3.6
Doubling) and was added over 86 minutes.

(Formation of External Low Iodity Phase-Shell Phase) Next, <H-2> and <S> while maintaining the pH at 10.1 and the pH at 6.0.
-2> was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a broad distribution of 12.4% and a silver iodide content of 8.5 mol%.

[0096] In the above emulsion preparation method, the average grain size and the silver iodide content differ in the same manner except that the average grain size of seed crystals, temperature conditions, pAg, pH, flow rate, addition time, and halide composition are changed. Each emulsion was prepared separately.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene, 1
-Phenyl-5-mercaptotetrazole was added.

[0098]

[Chemical 32]

[0099]

[Chemical 33]

[0100]

[Chemical 34]

[0101]

[Chemical 35]

[0102]

[Chemical 36]

[0103]

[Chemical 37]

[0104]

[Chemical 38]

[0105]

[Chemical Formula 39] In addition, the above-mentioned photosensitive material sample 201 is the compound Su-
1, Su-2, viscosity modifier, hardener H-1, H-2, stabilizer ST-1, antifoggant AF-1, AF-2 (weight average molecular weight 10,000 and 1,100,000), Dyes AI-1, AI-2 and compound DI-1 (9.4 mg /
m ² ) is contained.

[0106]

[Chemical 40]

[0107]

[Chemical 41]

Photosensitive material sample 20 produced as described above
1 was exposed to white light through a step wedge for sensitometry and processed under the following conditions.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer water 800 ml potassium carbonate 30 g sodium hydrogen carbonate 2.5 g potassium sulfite 3.0 g sodium bromide 1.3 g potassium iodide 1.2 mg hydroxylamine sulfate 2.5 g sodium chloride 0.6 g 4-amino-3-methyl-N -Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter, and potassium hydroxide or 20%
Adjust to pH 10.06 with sulfuric acid.

Color developing replenisher liquid 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β- Hydroxylethyl) aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water is added to make 1 liter, potassium hydroxide or 20%
Adjust to pH 10.18 with sulfuric acid.

Bleaching solution Water 700 ml 1,3 Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 liter, and ammonia water or Adjust to pH 4.4 with glacial acetic acid.

Bleaching Replenisher Water 700 ml 1,3 Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g pH 4 using ammonia water or glacial acetic acid. After adjusting to 0, add water to make 1 liter.

Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 with aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher water 800 ml ammonium thiocyanate 150 g ammonium thiosulfate 180 g sodium sulfite 20 g ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

[0116] stabilizing solution and stabilizing replenisher water _{900ml C 8 H 17 - (C} 6 H 4) -O- (C 2 H 4 O) 10 H 2.0 g dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-benz Isothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml After adding water to make 1 liter, ammonia water or 50%
The pH was adjusted to 8.5 with sulfuric acid.

Further, Sample 2 was prepared in the same manner as in Sample 201 except that the yellow couplers (Y-1a) in the ninth and tenth layers of Sample 201 were changed as shown in Table 4.
Created 02-212. The addition amount was adjusted to be the same as the addition amount in Sample 201.

Each of these samples was exposed to white light with a ratio of 1/100.
After second-wedge exposure and color development according to the above processing steps, maximum density Dmax and minimum density Dmin were measured using an optical density system (PDA-65 type manufactured by Konica). The results are shown in Table 4.

[0119]

[Table 4] From the results shown in Table 4, all the samples using the coupler of the present invention had a higher maximum color density than the comparative sample,
It can be seen that an image with less fog is formed.

Example 3 One side (surface) of triacetyl cellulose film support
Was subjected to an undercoating treatment, and then the support was sandwiched between the support and a surface opposite to the surface subjected to the undercoating treatment (back surface) to form a layer having the following composition from the support side.

A multilayer color photographic light-sensitive material sample 301 was prepared by sequentially forming each layer having the composition shown below from the support side on the surface of the triacetyl cellulose film support which was subjected to the undercoating. The addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified.

First layer (antihalation layer) Black colloidal silver 0.24 g UV absorber U-1 0.14 g UV absorber U-2 0.072 g UV absorber U-3 0.072 g UV absorber U-4 0.072 g High boiling point Solvent O-1 0.31 g High boiling point solvent O-2 0.098 g Poly-N-vinylpyrrolidone 0.15 g Gelatin 2.02 g Second layer (intermediate layer) High boiling point solvent O-3 0.011 g Gelatin 1.17 g Third layer (low sensitivity red sensitive layer) ) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (3.0 mol% of silver iodide, average particle size 0.30 μm) 0.60 g Coupler C-1 0.37 g High boiling point solvent O- 2 0.093 g Poly-N-vinylpyrrolidone 0.074 g Gelatin 1.35 g Fourth layer (high-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (3.0 mol of silver iodide) %, Average particle size 0.80 μm) 0.60 g Coupler C-1 0.85 g High boiling point solvent O-2 0.21 g Poly N vinyl Lupyrrolidone 0.093 g Gelatin 1.56 g Fifth layer (intermediate layer) Color mixing inhibitor AS-1 0.20 g High boiling point solvent O-3 0.25 g Matting agent MA-1 0.0091 g Gelatin 1.35 g Sixth layer (low sensitivity green sensitive layer) ) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye S-3 (silver iodide 3.0 mol%, average particle size 0.30 μm) 0.70 g coupler M-1 0.31 g coupler M-2 0.076 g high boiling solvent O-3 0.059 g Poly-N-vinylpyrrolidone 0.074 g Gelatin 1.29 g Seventh layer (high-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye S-3 (3.0 mol% silver iodide, Average particle size 0.80 μm) 0.70 g Coupler M-1 0.80 g Coupler M-2 0.19 g Color mixing inhibitor AS-1 0.055 g High boiling point solvent O-3 0.16 g Poly N vinylpyrrolidone 0.12 g Gelatin 1.91 g Eighth layer (intermediate layer) Layer) Gelatin 0.90 g 9th layer (yellow filter layer) Yellow colloidal silver 0.11 g mixed Inhibitor AS-1 0.068 g High boiling point solvent O-3 0.085 g Matting agent MA-1 0.012 g Gelatin 0.68 g 10th layer (low sensitivity blue sensitive layer) Iodine spectrally sensitized with blue sensitizing dye S-4 Silver bromide emulsion (3.0 mol% silver iodide, average particle size 0.30 μm) 0.70 g Coupler Y-2 0.86 g Image stabilizer G-1 0.012 g High boiling point solvent O-3 0.22 g Poly N vinylpyrrolidone 0.078 g Compound F -1 0.020 g Compound F-2 0.040 g Gelatin 1.09 g 11th layer (high-sensitivity blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-4 (silver iodide 3.0 mol%, average Particle size 0.85 μm) 0.70 g Coupler Y-2 1.24 g Image stabilizer G-1 0.017 g High boiling point solvent O-3 0.31 g Poly N vinylpyrrolidone 0.10 g Compound F-1 0.039 g Compound F-2 0.077 g Gelatin 1.73 g 12th layer (protective layer-1) Non-photosensitive fine grain silver iodobromide (silver iodide 1.0 mol%, average grain size 0.08 μm) 0.075 g Outer line absorber U-1 0.048g UV absorber U-2 0.024g UV absorber U-3 0.024g UV absorber U-4 0.024g High boiling point solvent O-1 0.13 g High boiling point solvent O-2 0.13 g Compound F -1 0.075 g Compound F-2 0.15 g Gelatin 1.2 g 13th layer (protective layer-2) Sliding agent WAX-1 0.041 g Matting agent MA-2 0.0090 g Matting agent MA-3 0.051 g Surfactant SU-1 0.0036 g Gelatin 0.55 g (Note: The weight average molecular weight of poly-N-vinylpyrrolidone used in each layer is 350,000. )

The above-mentioned light-sensitive material sample 301 further comprises gelatin hardeners H-1, H-2, H-3 and water-soluble dye AI.
-1, AI-2, AI-3, compound DI-1, stabilizer S
T-1 and the antifoggant AF-1 were appropriately added as needed.

The silver halide emulsions used in each light-sensitive layer were all monodisperse emulsions having a distribution of 20% or less.

Each emulsion was desalted and washed with water, and then subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to spectrally sensitize the silver halide emulsion used for each light-sensitive layer. For this purpose, each sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

The width of the distribution is defined by the following formula.

[0127]

[Equation 2]

[0128]

[Chemical 42]

[0129]

[Chemical 43]

[0130]

[Chemical 44]

[0131]

[Chemical formula 45]

[0132]

[Chemical formula 46]

[0133]

[Chemical 47]

[0134]

[Chemical 48]

The light-sensitive material sample 201 was exposed to white light through a sensitometric measurement step wedge, and was subjected to the following development processing. Treatment process Treatment time Treatment temperature 1st development 6 minutes 38 ℃ Water wash 2 minutes 38 ℃ Reversal 2 minutes 38 ℃ Color development 6 minutes 38 ℃ Adjustment 2 minutes 38 ℃ Bleach 6 minutes 38 ℃ Settlement 4 minutes 38 ℃ Water Washing 4 minutes 38 ℃ Stabilization 1 minute Drying at room temperature

The composition of the processing liquid used in the above processing step is as follows. First developer sodium tetrapolyphosphate 2 g sodium sulfite 20 g hydroquinone monosulfonate 30 g sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to bring the pH to 9.60, 1000 ml.

Inversion solution Nitrilotrimethylenephosphonic acid-6 sodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to obtain a pH of 5.75, 1000 ml. I gave it up.

Color developer Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium triphosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazic acid 1.5 g N -Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Water was added to bring the pH to 11.70, 1000 ml.

Preparation liquid Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water was added to adjust pH to 6.15 and 1000 ml.

Bleaching liquid Sodium ethylenediaminetetraacetate (dihydrate) 2 g Ethylenediaminetetraacetate iron (III) ammonium (dihydrate) 120 g Ammonium bromide 100 g Water was added to bring the pH to 5.65, 1000 ml.

Fixing solution Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water was added to bring the pH to 6.60, 1000 ml.

Stabilizer Formalin (37% by weight) 5 ml Conidax (manufactured by Konica Corporation) 5 ml Water was added to make pH 7.00, 1000 ml.

Then, in the preparation of Sample 301, the yellow coupler (Y-2) of the 10th and 11th layers was changed to the yellow coupler of the present invention to prepare Samples 302 to 306 of the present invention. It shows in Table 5.

[0144]

[Table 5] After the color development processing was performed according to the above-mentioned processing steps, the maximum color density Dmax and the minimum color density Dmin were measured. From the results obtained, it was found that the sample using the coupler of the present invention forms an image with high maximum color density and less fog.

[0145]

As described in detail above, according to the present invention, it can be produced at low cost, is excellent in color developing property, color reproducibility and image storability, and is suitable for low boiling point and high boiling point solvents used for dispersing a coupler. It was possible to provide a silver halide color photographic light-sensitive material containing a 2-equivalent yellow coupler having high solubility and excellent dispersion stability.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is represented by the following general formula [I]. A silver halide color photographic light-sensitive material containing 2 equivalents of a yellow coupler. [Chemical 1] [Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
Represents a cycloalkyl group and an aryl group, R ₃ represents an alkyl group, a cycloalkyl group or an aryl group,
R ₄ represents a substituent, and R ₅ and R ₆ represent a hydrogen atom, an alkyl group, a cycloalkyl group and an aryl group, respectively. n represents an integer from 0 to 4. ]