JPH10123684A - Silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To minimize the reduction in density of a color image even by processing with a fatigued bleaching solution by containing a specified cyan coupler in an emulsion layer. SOLUTION: In a photographic material having at least one silver halide emulsion layer on a support body, at least one cyan coupler represented by the formula is contained in at least one emulsion layer. In the formula, R1 represents a hydrogen bonding group, and R2 and R3 represent a substituent. (n) represents an integer of 0 to 3, and when (n) is 2 or more, R2 and R3 may be the same or different. X represents hydrogen atom or a group detachable by the coupling reaction with an oxide body of coloring developing agent. The hydrogen bonding group represented by R1 means a group containing an active hydrogen atom hydrogen-bonded with the oxygen atom of the carbonyl group in 9-position of pyrazoloquinazolone nucleus. The substituted atom or substituent represesnted by R2 and R3 is not particularly limited, and examples thereof include alkyl, anyl, anilino, acylamino, sulfonamide or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material containing a cyan coupler.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material) is subjected to color development after exposure, whereby a paraphenylenediamine-based color developing agent reacts with a coupler to form a dye. As a result, a color image is formed.

In general, in this photographic method, a color reproduction method based on a subtractive color method is used, and a yellow, magenta, and cyan color image is formed.

As the cyan dye-forming couplers (cyan couplers), phenols and naphthols are typical. Among them, naphthols can have a sufficiently long wave and have high coupling reactivity. Used for

Up to now, naphthols substituted with a carbamoyl group at the 2-position have been used. However, this type of cyan dye is liable to undergo reduction and fading, and the color density is reduced when treated with a tired bleaching solution. there were. On the other hand, a technique for improving the above problem by introducing a new substituent at the 5-position of 1-naphthols is disclosed in
No. 237448, No. 61-153640, No. 63-2
No. 08042. Although the compounds described in the above-mentioned patents show improvement in reduction and fading of the cyan dye and reduction in the concentration in the treatment with the fatigue bleaching solution, the cyan dye has insufficient fastness to heat, humidity and light, and improvement is desired. It is rare. Also, JP-A-1-121095,
1-183658, 1-73037, 1-2
No. 06339 describes a pyrazoloquinazolone nucleus cyan coupler as a coupler having excellent fastness to heat and light. However, these compounds have not reached sufficiently satisfactory levels for the reduction and fading of the dye and the reduction in the concentration in the fatigue bleaching solution.

The inventors of the present invention have conducted various studies on the above problems, and as a result, those having a hydrogen bonding group in the pyrazoloquinazolone nucleus have been found to have a reduced concentration in a fatigue bleaching solution and to have fastness to heat and light. The inventors have found that they give favorable results in this respect, and have led to the present invention.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material containing a cyan coupler which causes little reduction in the density of a color image even when processed in a fatigue bleaching solution.

A second object of the present invention is to provide a silver halide photographic material containing a cyan coupler in which the cyan dye formed has improved fastness to heat and light.

A third object of the present invention is to provide a silver halide photographic light-sensitive material containing a cyan coupler in which a cyan dye to be formed has preferable spectral characteristics, has a high coloring density, and has improved coloring properties.

[0010]

The above object of the present invention is attained by the following constitutions.

1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains at least one cyan coupler represented by the following general formula [1]. A silver halide photographic light-sensitive material, characterized in that:

[0012]

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In the formula, R ₁ represents a hydrogen bonding group, and R ₂ and R ₃ represent a substituent. n represents an integer of 0 to 3;
Is 2 or more, each may be the same or different. Also, R ₁ and R ₃ may form a ring. X represents a hydrogen atom or a group which is eliminated by a coupling reaction with an oxidized form of a color developing agent.

Hereinafter, the present invention will be described in detail.

In the general formula [1], the hydrogen-bonding group represented by R ₁ is a group containing an active hydrogen atom hydrogen-bonding to the oxygen atom of the 9-position carbonyl group of the pyrazoloquinazolone nucleus. Represent. Specific examples of the preferred hydrogen-bonding group represented by R ₁ are —NHCOR ₄ , —NHSO ₂ R ₄ , and —NHSO
R ₄ and —OH (R ₄ represents a hydrogen atom or a substituent, and preferably includes an alkyl group, an aryl group, a heterocyclic group, and the like).

In the general formula [1], the substituent atoms and substituents represented by R ₂ and R ₃ are not particularly limited, but are typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio. , Alkenyl, cycloalkyl and the like, but in addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro, sulfonic acid, etc. And spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R ₂ and R ₃ preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R ₂ and R ₃ is preferably a phenyl group.

The acylamino group represented by R ₂ and R ₃ includes an alkylcarbonylamino group, an arylcarbonylamino group and the like.

Examples of the sulfonamide group represented by R ₂ and R ₃ include an alkylsulfonylamino group and an arylsulfonylamino group.

An alkylthio group represented by R ₂ and R ₃ ,
Examples of the alkyl component and the aryl component in the arylthio group include the alkyl groups and aryl groups represented by R ₂ and R ₃ .

The alkenyl group represented by R ₂ and R ₃ is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. However, it may be branched.

The cycloalkenyl group represented by R ₂ and R ₃ preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

Examples of the sulfonyl group represented by R ₂ and R ₃ include an alkylsulfonyl group and an arylsulfonyl group;
As a sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, etc .; As a phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group Etc .; as the carbamoyl group, an alkylcarbamoyl group,
Arylcarbamoyl group, etc .; sulfamoyl group as alkylsulfamoyl group, arylsulfamoyl group, etc .; acyloxy group as alkylcarbonyloxy group, arylcarbonyloxy group, etc .; carbamoyloxy group as alkylcarbamoyloxy group, arylcarbamoyloxy group A ureido group such as an alkylureido group or an arylureido group; a sulfamoylamino group such as an alkylsulfamoylamino group or an arylsulfamoylamino group;
Preferred is a 7-membered one, specifically a 2-furyl group, 2-
A thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, a 1-pyrrolyl group, a 1-tetrazolyl group and the like; a heterocyclic oxy group having a 5- to 7-membered heterocyclic ring is preferable, for example, 3, 4, 5, 6-tetrahydropyranyl-
2-oxy group, 1-phenyltetrazol-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, , 4-Diphenoxy-1,3,5-
Triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group, 3-heptadecylsuccinimide group, phthalimide group and glutarimide group Spiro [3,3] heptane-1-yl as a spiro compound residue; bicyclo [2,2,1] heptane-1- as a bridged hydrocarbon compound group
Yl, tricyclo [3,3,1,1 ^37] decan-1-yl, 7,7-dimethyl - bicyclo [2,2,1] heptane-1-yl, and the like.

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

In the general formula [1], X is bonded to an active site and is an atom or group which can be removed by a reaction with an oxidized form of a color developing agent, for example, a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom) , Fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonyl Thio, acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom,
Examples include groups such as alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and alkyl, and a halogen atom is preferable. Of these, particularly preferred as X are a hydrogen atom and a chlorine atom.

Hereinafter, typical specific examples of the cyan coupler represented by the general formula [1] of the present invention are shown, but the present invention is not limited thereto.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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Compound Examples 1-29 The couplers of the present invention exemplified above are described in US Pat. No. 3,171,740.
Nos. 4,261,996 and 4,24
The compound can be synthesized with reference to the method described in 7,555.

Next, typical methods for synthesizing the coupler of the present invention will be described.

[Synthesis Example 1 (Synthesis of Exemplified Compound 1 of the Present Invention)]

[0037]

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Synthesis Example 1 3-nitrophthalic anhydride (115 g) was treated with methanol (180 m).
and heated to reflux for about 2 hours in a water bath. After removing the solvent, the mixture was allowed to stand at room temperature for 2 to 3 hours to precipitate white crystals, which were collected by filtration and further recrystallized with water.
6 g (95%) were obtained.

To 15 g of 2 was added 60 ml of thionyl chloride, and the mixture was refluxed for 15 minutes until the solid was dissolved. After removing thionyl chloride, dry acetone was added to dissolve the mixture, followed by ice cooling. A solution obtained by dissolving 16.55 g of sodium azide in 60 ml of water was added dropwise, stirred for 15 minutes, and diluted with water to precipitate a white solid. This was collected by filtration, washed with water, and used for the next reaction in a wet state.

The above-mentioned white solid was dissolved in a mixed solvent of 73 g of acetic acid / 25 ml of water and refluxed for 30 minutes. The reaction solution was colored orange, and water was added to the solution to dilute it. A solid was precipitated. The solid was collected by filtration, recrystallized from methanol, and dried.
8.5 g (65%) were obtained.

To 5 g of 3 were added 50 ml of toluene and 1.5 g of hydrazine monohydrate, and the mixture was refluxed for 9 hours. The toluene layer was removed, and ethanol was added to precipitate an ocher solid, which was collected by filtration to obtain 2.32 g (54%) of 4. Dissolve and heat to reflux for 1.5 hours. 3.4 g of sodium carbonate was added, the mixture was further heated under reflux, allowed to cool, and then the reaction solution was acidified with concentrated hydrochloric acid. A yellow solid precipitated, which was collected by filtration, washed with water, and recrystallized from methanol to give 5 to 6.5.
g (79%).

3 g of 5 were suspended in 20 ml of thionyl chloride, and 2 drops of pyridine were added. After stirring at room temperature for 24 hours, thionyl chloride was completely removed, the obtained solid was suspended in acetonitrile, cooled with ice, and 4 g of amine was added dropwise. After stirring at room temperature for 6 hours, the solvent was removed, extracted with ethyl acetate, purified by column chromatography, and 3.1 g of 6 was obtained.
(50%).

3 g of 6 was dissolved in 50 ml of ethanol,
A catalytic amount of palladium carbon was added and hydrogenated. After completion of the reaction, the palladium carbon was removed by filtration, the reaction solution was concentrated, dissolved in 50 ml of acetonitrile, 0.4 g of chloropropionic chloride was slowly added dropwise, and the mixture was stirred at room temperature overnight. Acetonitrile was removed, extracted with ethyl acetate, and purified by column chromatography to obtain Exemplified Compound 1.

The obtained compound was confirmed to be the above pyrazoloquinazolone coupler by NMR and Mass spectra.

The couplers of the present invention exemplified above can be synthesized in the same manner with reference to the above synthesis examples.

In the present invention, the cyan coupler represented by the general formula [1] is contained in at least one layer of the red-sensitive silver halide emulsion layer.

In order to incorporate the cyan coupler of the present invention into a silver halide emulsion layer, a conventionally known method, for example, a known high boiling solvent such as dibutyl phthalate or tricresyl phosphate, and butyl acetate, ethyl acetate or the like can be used. After dissolving the cyan coupler of the present invention in a mixed solution of a low-boiling solvent or a solvent containing only a low-boiling solvent, the mixture is mixed with a gelatin aqueous solution containing a surfactant, and then mixed with a high-speed rotary mixer or a colloid mill or ultrasonic dispersion. After emulsifying and dispersing using an emulsifier, a method of directly adding it to the emulsion can be employed. Alternatively, the emulsified dispersion may be set, then cut into pieces, washed with water, and then added to the emulsion.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers 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 color photographic light-sensitive material.

Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, and a hardening agent are obtained by coupling with a colored coupler having a color correcting effect, a competitive coupler and an oxidized form of a developing agent. Compounds that release photographically useful fragments can be used, such as filming agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

The light-sensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an anti-irradiation layer. In these layers and / or emulsion layers,
A dye which flows out of the light-sensitive material or is bleached during the development processing may be contained. Photosensitive materials include formalin scavengers, fluorescent brighteners, matting agents, lubricants, image stabilizers, surfactants, color fog inhibitors, development accelerators,
A development retarder and a bleaching accelerator can be added.

As a 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.

[0055]

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

Example 1 <Evaluation of single-layer coating> The following comparative coupler C-1, 10 g, dioctyl phthalate (DOP) 10 g and ethyl acetate 1
0 ml was heated to 50 ° C. to completely dissolve the solution, and 10 g of gelatin and 0.4 g of alkanol XC (sodium diisopropylnaphthalenesulfonate manufactured by Dupont) were added.
Was mixed with 100 ml of an aqueous solution containing, and then finely emulsified and dispersed by ultrasonic waves. 35 g of silver iodobromide was added to this coupler dispersion.
And 400 g of photographic emulsion containing 40 g of gelatin,
2,4-dichloro-6-hydroxy-5 as a hardener
-After adding 40 ml of a 2% aqueous solution of sodium triazine, the pH was adjusted to 6.0, and the solution was uniformly applied on a triacetyl cellulose-based film base that had been subbed. Next, Samples 2 to 13 were prepared in the same manner as in Sample 1, except that the same molar couplers shown in Table 1 were used instead of Comparative Coupler C-1.

Each of the sample Nos. 1 to
After subjecting No. 13 to wedge exposure for 1/100 second using red light, the following developing processes A and B were performed.

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. However, in processing A, the processing solution in the bleaching step is the following bleaching liquid A, and in processing B, the processing liquid in the bleaching step is the following bleaching liquid B.

<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 0.0 g anhydrous potassium carbonate 37.5 g potassium bromide 1.3 g nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g potassium hydroxide 1.0 g Add water to make 1 liter (pH = 10.2) .

<Bleaching Solution A> Ammonium iron (III) ethylenediaminetetraacetate 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Water was added to make 1 liter, and the pH was adjusted using aqueous ammonia.
= 6.0.

<Bleach B> The same composition as Bleach A except that 2.5 g of sodium hydrosulfite was added to Bleach A per liter.

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium meta sulfite 2.3 g Water was added to make 1 liter, and the pH was adjusted to 6.0 using acetic acid.
Adjust to

<Stabilizing Solution> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1 liter.

The obtained sample No. Samples Nos. 1 to 13 were processed in accordance with the above color development process, and the resulting dye images were measured for maximum density with red light using an optical densitometer (PDA-65, manufactured by Konica Corporation). Incidentally, development processing B
Is a model of the fatigue bleaching solution.

The maximum concentration is a value when the bleaching solution A is used.

The reproducibility was calculated by the following equation.

Recolorability (%) = (maximum density when using bleaching solution B) / (maximum density when using bleaching solution A) × 100 It was expressed as the change in density at the maximum density part after irradiation with a fade meter at 70,000 lux for 3 days. The heat resistance was represented by the density change of the maximum density part after the sample that had been processed by the development processing A was stored at 40 ° C. and 80% (relative humidity) for 6 days.

Table 1 shows the results. The structural formula of the comparative cyan coupler is also shown below.

[0069]

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[0070]

[Table 1]

As is clear from Table 1, C-1 has poor color reproducibility, and the color reproducibility of C-3 and C-5 is slightly improved, but not at a sufficient level. C-2 and C-4 have good color reproducibility, but have insufficient light fastness. All of the samples using the cyan coupler of the present invention have good recolorability and light resistance,
Excellent heat resistance. Also, it can be seen that the maximum density is higher than that of the comparative coupler.

[0072]

As demonstrated in the Examples, the silver halide photographic light-sensitive material according to the present invention has a small decrease in the density of a color image even when processed in a fatigue bleaching solution, and the fastness of the formed cyan dye to heat and light. Is improved, and the formed cyan dye has preferable spectral characteristics, a high color density, and an excellent effect of improved color development.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material, characterized in that at least one of the silver halide emulsion layers contains at least one cyan coupler represented by the following general formula [1]. Embedded image [In the formula, R ₁ represents a hydrogen bonding group, and R ₂ and R ₃ represent a substituent. n represents an integer of 0 to 3, and when n is 2 or more, each may be the same or different.
Also, R ₁ and R ₃ may form a ring. X is a coupling reaction with a hydrogen atom or an oxidized form of a color developing agent,
Represents a leaving group. ]