JPH10148918A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide color photographic sensitive good in sharpness and superior in color reproduction performance by incorporating a specified compound. SOLUTION: The photosensitive material contains the compound represented by the formula in which Coup is a coupling component to be allowed to release a (Time)n and is following group by reaction with the oxidation product of a developing agent and Coup from a mobile dye and substantially does not contribute to the image formation of the photosensitive material; Time is a timing group for releasing the DI-CO2 R group after being released from Coup; (n) is 1 or 2 and when (n) is 2, 2 of Time may be same or different; DI is a development inhibitor having a mercaptoazole structure combined through the S atom with Time; R is a substituted alkyl group; and CO2 R is an alkoxycarbonyl group substituted to an optional position of the development inhibitor group of a mercaptoazole structure.

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 material, and more particularly to a silver halide color photographic material having improved color reproducibility and sharpness.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand for the development of color light-sensitive materials having high sensitivity and excellent sharpness and color reproducibility.

[0003] As a means for improving sharpness, DIR compounds which react with an oxidized form of a color developing agent to release a development inhibitor are known. It is well known that by containing this in an emulsion, color reproducibility and sharpness are improved by edge effects between layers and within the layer.

However, since these DIR compounds usually have a diffusion-resistant group (ballast group) on the coupler mother nucleus, the dye obtained by reacting with the oxidized color developing agent remains in the photographic element. I do. Therefore, when the DIR compound is added to a coupler-containing layer having a different hue by increasing the addition amount thereof, color turbidity occurs, which is a serious disadvantage that color reproduction is not preferable.

On the other hand, as means for solving the above-described color turbidity,
Japanese Patent Application Laid-Open No. 58-1629 discloses a DIR compound which causes a dye formed by reacting with a color developing agent to flow out into a processing solution.
No. 49, 63-37350 and EP 443,530
No. etc. Indeed, it has been found that the use of these DIR compounds solves the above problem of color turbidity. However, the DIR compound has low reactivity,
The DIR compound itself is not yet sufficient in terms of edge effect and interlayer effect.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic material having excellent sharpness and excellent color reproducibility.

[0007]

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

(1) A silver halide color photographic material comprising a compound represented by the following formula (A-1):

[0009]

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In the formula, Coup reacts with an oxidized developing agent to release a group of (Time) n or less and forms a mobile dye, contributing to a substantial image of a silver halide color photographic light-sensitive material. Represents a coupling component that does not
e represents a timing group that releases DI-CO ₂ R after being released from Coup, and n represents 1 or 2. n is 2
In this case, the two Times may be the same or different. DI represents a mercaptoazole skeleton inhibitor residue bonded to Time by a sulfur atom, and R represents a substituted alkyl group. In the general formula (A-1), Coup reacts with an oxidized developing agent to release a group of (Time) n or less and forms a mobile dye, thereby realizing a silver halide color photographic material. Represents a coupling component that does not contribute to the target image. Such a coupling component is disclosed in, for example, JP-A-58-160.
No. 954, a coupler residue having an alkali-soluble group. Of the various coupler residues described in the patent, a coupling component of a naphthol nucleus is preferable from the viewpoint of coupling activity. Particularly preferred coupling components include naphthol nucleus coupling components described in JP-A-58-162949 and JP-A-63-37350.

In the general formula (A-1), Time is C
It represents a timing group which releases DI-CO ₂ R after release from oup. Examples of such a timing group include a timing group using an intramolecular nucleophilic substitution reaction described in JP-A-54-145135, and a timing group described in JP-A-5-145135.
And timing groups utilizing electron transfer along a conjugated system described in JP-A-6-114946 and JP-A-57-154234. Of these timing groups, a so-called quinone methide type timing group which releases a photographically useful group with the generation of quinone methide by electron transfer along a conjugated system is preferable. n represents 1 or 2, and when n is 2, two Times may be the same or different. Preferably, n = 1.

The compound represented by the general formula (A-1)
A hydrophobic group having a high molecular weight called a so-called ballast group may or may not be substituted on the timing group represented by im. However, when the ballast group is not substituted on the Time, it is preferable that the carboxyl group and the sulfo group are not substituted on the coupling component represented by Coup.

In the general formula (A-1), DI represents a mercaptoazole skeleton development inhibitor residue bonded to Time by a sulfur atom. Preferred development inhibitors include, for example, 5-mercaptotetrazole compounds, 2-mercapto-1,3,4-oxadiazole compounds, mercaptobenzothiazole compounds (eg, 2-mercaptobenzothiazole and the like), mercaptobenzimidazole Compounds, mercaptobenzoxazole compounds and the like. In formula (A-1), preferred as DI are 2-mercapto-1,3,4-oxadiazole-based compound and 5-mercaptotetrazole-based compound.

In the general formula (A-1), CO ₂ R represents an alkoxycarbonyl group substituted at an arbitrary position of the development inhibitor residue of the mercaptoazole skeleton, and R represents an alkyl group having a substituent. . The carbon number of the alkyl group represented by R is preferably 8 or less, particularly preferably 4 or less. Examples of the substituent on R include any substituent (eg, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group, an acyl group) excluding an alkali-soluble group (eg, a carboxyl group, a sulfo group, etc.). , A sulfonyl group, an aryl group, a heterocyclic group, a nitro group, etc.).

In the general formula (A-1), DI-CO ₂ R
The inhibitor residues represented by are shown below, but are not limited thereto.

[0016]

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In the formula (A-1), particularly preferred compounds are those represented by the following formulas (A-2), (A-3) or (A-
4).

[0018]

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In the general formula (A-2), L represents 4 carbon atoms.
Represents the following substituted or unsubstituted alkylene group;
Represents a substituted or unsubstituted alkyl group having 4 or less carbon atoms. However, the sum of the carbon numbers of L and R 'is 4 or less. DI
—CO ₂ R has the same meaning as in formula (A-1).

In the general formulas (A-3) and (A-4), L represents a substituted or unsubstituted alkylene group having 4 or less carbon atoms, and R ″ represents a hydrogen atom or a substituted or unsubstituted alkylene group having 4 or less carbon atoms. Or an unsubstituted alkyl group, provided that the sum of the carbon numbers of L and R ″ is 4 or less. The general formula (A-
In 3) and (A-4), X represents a ballast group having 8 or more carbon atoms, and DI-CO ₂ R has the same meaning as in formula (A-1).

The following are typical examples of the compound represented by formula (A-1) of the present invention, but the invention is not limited thereto.

[0022]

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[0023]

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[0024]

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The following are typical examples of the synthesis of the compounds of the present invention.

Synthesis Example 1 Synthesis of Exemplified Compound A9

[0027]

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(1) Synthesis of Intermediate (3) 370 g of Intermediate (1) and 127.3 g of β-alanine ethyl ester (2) were added to 2000 ml of dioxane, and dicyclohexylcarbodiimide (DC) was added under ice cooling.
C) 206.3 g were added. After reacting at room temperature for 90 minutes, the reaction was performed at 50 ° C. for 90 minutes. After cooling, dioxane was distilled off under reduced pressure except for the precipitated urea. The residue was dissolved in ethyl acetate and washed with water and dilute hydrochloric acid. After drying over magnesium sulfate, ethyl acetate was distilled off. The residue was recrystallized from ethyl acetate to obtain 350 g of the intermediate (3).

(2) Synthesis of Exemplified Compound A9 56.7 g of Intermediate (3) and 35.2 g of INH-13
Is added to 500 ml of acetone, and then potassium carbonate 1
8.2 g was added and reacted at room temperature for 4 hours. After the completion of the reaction, the mixture was extracted with ethyl acetate, and then washed with a 5% aqueous potassium carbonate solution and diluted hydrochloric acid. After drying over magnesium sulfate,
Ethyl acetate was distilled off. The residue was purified by silica gel column chromatography to obtain 73.1 g of Exemplified Compound A9. The structure was confirmed by NMR, IR and mass spectra.

Synthesis Example 2 Synthesis of Exemplified Compound A14

[0031]

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47.2 g of Exemplified Compound A9 was added to 100 parts of acetic acid.
The solution was dissolved in 0 ml, and 119.7 g of tin powder was added under water cooling. After reacting at room temperature for 1 hour, the reaction was performed at 60 ° C. for 2 hours. After the completion of the reaction, insolubles were filtered off, then water was added to the filtrate, and the mixture was extracted with ethyl acetate. After washing with a 5% aqueous potassium carbonate solution and drying over magnesium sulfate, ethyl acetate was distilled off. The obtained residue was used for the next reaction without purification.

42.6 g of the unpurified intermediate (5) was dissolved in 500 ml of acetonitrile, and 21.8 g of hexadecylsulfonyl chloride and 5.3 g of pyridine were added.
The reaction was continued for 6 hours under heating to reflux. After extraction with ethyl acetate, washing and drying, the solvent was distilled off. The residue was purified by silica gel column chromatography to give 34.3 g of Exemplified Compound A14. NM
The structure was confirmed by R, IR and mass spectra.

The DIR coupler according to the present invention can be contained in any layer of the photographic material, for example, a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer.
It is preferably used for a silver halide emulsion layer. More preferably, it is used for a blue-sensitive silver halide emulsion layer and / or a green-sensitive silver halide emulsion layer.

In order to incorporate the DIR coupler of the present invention into a hydrophilic colloid layer of a color light-sensitive material, for example, a known dibutyl phthalate, tricresyl phosphate,
A DIR coupler according to the present invention in a high-boiling solvent such as dinonylphenol or a mixed solution thereof with a low-boiling solvent such as butyl acetate or propionic acid, each alone,
Alternatively, after being dissolved together, mixed with a gelatin aqueous solution containing a surfactant, and then emulsified and dispersed using a high-speed rotating mixer or a colloid mill or an ultrasonic disperser, or directly added to the emulsion, Alternatively, a method in which the above emulsified dispersion is set, shredded, washed with water, and then added to the emulsion can be used.

The amount of the DIR coupler according to the present invention used is
The amount is preferably 0.0005 to 5.0 mol, more preferably 0.005 to 1.0 mol, per mol of silver halide.

The DIR coupler according to the present invention may be used alone or in combination of two or more.

As the silver halide emulsion for use in the silver halide color photographic light-sensitive material of the present invention, any conventional silver halide emulsion can be used. The emulsion is
Chemical sensitization can be performed by a conventional method, and optical sensitization can be performed in a desired wavelength region using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer.

A coupler is used in the emulsion layer of the silver halide color photographic light-sensitive material of the present invention. Further, a development accelerator is obtained by coupling with a colored coupler having a color correction effect, a competitive coupler and an oxidized form of a developing agent,
Photographically useful fragments such as bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fog agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers Release compounds can be used.

The silver halide color light-sensitive material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and an antiirradiation layer. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained. Further, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder and a bleaching accelerator may be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, generally known color photographic processing can be performed after exposure.

[0045]

EXAMPLES Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

In all of the following examples, the addition amount in the silver halide color photographic light-sensitive material is per 1 m ² unless otherwise specified. Silver halide is shown in terms of silver.

Example 1 A multilayer color photosensitive material sample 1 was prepared by sequentially forming layers having the following compositions on a triacetyl cellulose film support from the support side.

First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver Second layer: Intermediate layer (IL) Gelatin containing emulsified dispersion of 2,5-di-t-octylhydroquinone Layer Third Layer; Low-Sensitivity Red-Sensitive Silver Halide Emulsion Layer (RL-1) Monodisperse emulsion of AgBrI containing 0.30 μm in average particle size and 6 mol% of AgI (Emulsion I) 1.8 g Sensitizing Dye I Silver 1 6 × 10 ^-5 mol sensitizing dye II per mol of silver 1 × 10 ^-5 mol per mol of silver Cyan coupler (C-1) 0.06 mol per mol of silver Colored cyan coupler (CC-1) ) 0.003 mol per 1 mol of silver DIR compound (D-1) 0.0035 mol per 1 mol of silver Fourth layer; high-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size 0 Ag containing 0.5 μm, 7.0 mol% of AgI consisting rI monodisperse Emulsion (Emulsion II) 3 × 10 ^-5 mol sensitization against sensitizing dye I 1 mol of silver 1.3g sensitizing dye II 1 mol of silver relative to 1 × 10 ^-5 mol cyan coupler (C -1) 0.02 mol per mol of silver Colored cyan coupler (CC-1) 0.0015 mol per mol of silver DIR compound (D-1) 0.001 mol per mol of silver No. 5 Layer: Intermediate layer (IL) Same as the second layer, gelatin layer.

Sixth layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion I 1.5 g Sensitizing dye III 2.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV Silver 1 1.2 × 10 ^-5 mol per mol of magenta coupler (M-1) 0.050 mol per mol of silver 0.009 mol per mol of colored magenta coupler (CM-1) DIR compound ( D-1) 0.0010 mol per 1 mol of silver DIR compound (D-3) 0.0030 mol per 1 mol of silver Seventh layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion II 1.4 g Sensitizing dye III 1.5 × 10 ⁻⁵ mol per mol of silver Sensitizing dye IV 1.0 × 10 ⁻⁵ mol per mol of silver Magenta coupler (M-1) 1 mol of silver 0.020 mol per 1 mol of colored magenta coupler (CM-1) silver 0.0002 mol DIR compound (D-3) 0.0010 mol per 1 mol of silver Eighth layer; Yellow filter layer (YC-1) Emulsified dispersion of yellow colloidal silver and 2,5-di-t-octylhydroquinone Ninth layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion composed of AgBrI containing 0.48 μm in average particle size and 6 mol% of AgI (Emulsion III) 0.9 g sensitized Dye V 1.3 × 10 ⁻⁵ mol per mol of silver Yellow coupler (Y-1) 0.29 mol per mol of silver 10th layer; high-sensitivity blue-sensitive silver halide emulsion layer (BH-1) ) Monodisperse emulsion of AgBrI containing 0.8 μm of average particle size and 15 mol% of AgI (Emulsion IV) 0.5 g of sensitizing dye V 1 × 10 ⁻⁵ mol per mol of silver Yellow coupler (Y-1) silver 0.08 per mole Mol DIR compound (D-2) 0.005 mol per mol of silver 11th layer; first protective layer (Pro-1) silver iodobromide (AgI 1 mol%, average particle size 0.07 μm),
Gelatin layer containing ultraviolet absorbers UV-1 and UV-2 Twelfth layer; second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (1.5 μm in diameter) and formalin scavenger (HS-1).

In each layer, a gelatin hardener (H-1) and a surfactant were added in addition to the above composition.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; anhydro-9-ethyl- 3,3'-di-
(Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide sensitizing dye III; anhydro-5,5'-diphenyl-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide sensitizing dye IV; anhydro-9-ethyl-3,3'-di-
(3-sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide sensitizing dye V; anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo- 5'-methoxythiocyanine hydroxide

[0053]

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[0054]

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[0055]

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[0056]

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Further, Samples 2 to 7 were prepared in the same manner as in Sample 1, except that the DIR compound (D-2) in the tenth layer of Sample 1 was replaced with an DIR compound shown in Table 1 in an equimolar amount. Produced.

Each of the samples thus prepared was exposed to wedges using blue light, color-developed by the following processing steps, and the sensitivity and gamma of the blue photosensitive layer were measured.

The red density was measured at the Dmax portion of the blue density. Table 1 shows the relative values when the red density of Sample 1 was set to 100.

At the same time, the image sharpness was also measured. The sharpness was determined by measuring the MTF of the dye image and indicating the relative value of the MTF of 30 lines / mm (sample 1 was taken as 100). Table 1 shows the results
Shown in

Processing step (38 ° C.) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in the process is as follows.

[Color developing solution] 4-amino-3-methyl-N-ethyl-N-β-hydroxyethyl aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter.

[Bleaching solution] Ammonium iron (III) ethylenediaminetetraacetate 100 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Add water to make 1 liter, and adjust the pH using aqueous ammonia.
Adjust to 6.0.

[Fixing Solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 with acetic acid.

[Stabilizing Solution] Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konica Corporation) 7.5 ml Make up to 1 liter by adding water.

[0066]

[Table 1]

[0067]

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As is clear from Table 1, Sample No. 2 shows that although the gamma lowering effect and the sharpness improving effect are large, the increase in red density is large, so that color turbidity is large and color reproduction is not preferable. Sample No. 3 and No. 3
No. 4 has no increase in red density and is preferable in color reproduction, but it can be seen that the gamma lowering effect and the sharpness improving effect are small. On the other hand, the sample No. of the present invention. Nos. 5, 6, and 7 indicate that the dye formed from the DIR compound and the oxidized color developing agent reacts with the sulfite ion in the processing solution to be decolorized and flow out of the film, so that the increase in red density is small and the gamma is reduced. The effect and sharpness improving effect were large.

Example 2 A basic sample was prepared by coating the following layers on a triacetate base in the following order.

(1) As a cyan coupler, C-20.
Red-sensitive silver iodobromide emulsion layer containing 5 g, 2.4 g of gelatin and 1.6 g of silver halide (2) Intermediate gelatin containing 0.5 g of gelatin and 0.1 g of 2,5-di-t-octylhydroquinone Layer (3) Blue-sensitive silver iodobromide emulsion layer containing 1.70 g of Y-1 as a yellow coupler, 2.4 g of gelatin and 1.6 g of silver halide (4) Protective layer composed of 0.8 g of gelatin The above basic sample Among the constituent layers, a DIR compound was added to the third layer containing the yellow coupler as shown in Table 2,
A sample was prepared.

Each sample was divided into two parts, one of which was subjected to wedge exposure with white light, and the other was subjected to wedge exposure with red light.

Next, the same treatment as in Example 1 was performed.

For each sample, a gamma value was obtained from the characteristic curve of the cyan dye obtained by color development, and gamma (γR) by red exposure was changed to gamma (γ) by white exposure.
Table 2 shows the values (γR / γW) divided by W).

[0074]

[Table 2]

As is clear from Table 2, the sample using the compound of the present invention has a large γR / γW value and the conventional DI
A larger overlay effect was obtained than the sample using the R coupler.

[0076]

According to the present invention, a color photographic light-sensitive material having good sharpness and excellent color reproducibility can be provided.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (A-1). Embedded image [Wherein Coup reacts with the oxidized developing agent (Tim
e) represents a coupling component which releases a group of n or less, forms a mobile dye, and does not contribute to a substantial image of a silver halide color photographic light-sensitive material;
Represents a timing group that releases DI-CO ₂ R after being released from, and n represents 1 or 2. When n is 2, the two Times may be the same or different. DI represents a mercaptoazole skeleton inhibitor residue bonded to Time by a sulfur atom, and R represents a substituted alkyl group. ]