JPH07119992B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a halogenated compound containing a magenta coupler which forms a magenta dye image having high color-developing property and improved storability, particularly light fastness and formalin fastness. More specifically, it relates to a silver halide color photographic light-sensitive material containing a novel magenta coupler.

BACKGROUND OF THE INVENTION A coupler which has been conventionally put to practical use for forming a magenta dye is a pyrazolone type coupler, which has unfavorable side absorption, and has storage stability, particularly resistance to formalin gas (formalin resistance). ) Is scarce.

In order to improve the above problems, various 1H-pyrazolo [5,1-c] -1,2,4-triazole magenta couplers have been proposed so far. For example, U.S. Pat.No. 3,725,067
And British Patent Nos. 1,252,418 and 1,334,515.

The compounds described in any of the patents are, of course, superior to the pyrazolone-based magenta coupler in terms of side absorption, but the improvement in formalin resistance is insufficient, and there is almost no improvement in terms of color developability and light fastness of the image. . The compounds described in Research Disclosure No. 12443 cannot be put to practical use at all in terms of color developability. 1H-pyrazolo [5,1-c] -1, described in JP-A-58-42045
The 2,4-triazole type magenta coupler is remarkably improved in terms of improvement in formalin resistance and color development, but is hardly improved in light resistance.

The couplers described in JP-A-59-99437 and JP-A-59-125732 have also been improved in color forming property, but in terms of light resistance of dye images based on the described couplers, the improvement still remains.

In the technique described in JP-A-59-125732, the light resistance of an image is simply improved by the additive used in combination therewith. However, the coupler of Compound Example 19 described in JP-A-59-99437 has a slightly improved light resistance, but it is still insufficient.

In other words, 1H-pyrazolo [5,1], which has been attracting attention for its lack of by-absorption and high tolerance to formalin.
It can be said that the -c] -1,2,4-triazole type magenta coupler has not been improved in light resistance of a dye image.

Therefore, the present inventors have found that 1H-pyrazolo [5,1-c] -1,2,4
-Regarding the light resistance of the triazole-based magenta coupler,
As a result of diligent research, it was found that those having a certain substitution at the 6-position have good light resistance.

Therefore, the present invention is based on this finding.

[Object of the Invention] The object of the present invention is to have good formalin resistance without side absorption,
Moreover, it is to provide a silver halide color photographic light-sensitive material having high color development and excellent light resistance.

[Construction of the Invention] The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one layer of the silver halide emulsion has the general formula [I ] A silver halide photographic light-sensitive material characterized by containing a magenta coupler represented by

General formula [I] (In the formula, Y ₁ and Y ₂ may be the same or different and each represents a hydrogen atom, an alkyl group or a cycloalkyl group, and Y ₁ and Y ₂ are not both hydrogen atoms. Also
Y ₁ and Y ₂ are bonded to each other with a nitrogen atom to form a 5-membered or 6-membered structure.
May form a heterocycle. R ₁ represents a hydrogen atom or a substituent. ) The alkyl group represented by Y ₁ and Y ₂ in the general formula [I] is an alkyl group having 1 to 20 carbon atoms (methyl, ethyl, propyl, i-propyl, butyl, i-butyl, pentyl, hexyl, heptyl). , Octyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl groups, etc.),
Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

Examples of the 5- or 6-membered heterocyclic group in which Y ₁ and Y ₂ are bonded to each other to form with a nitrogen atom include the following.

The alkyl group, cycloalkyl group, and heterocyclic group represented by Y ₁ and Y ₂ may further have a substituent, and the substituent includes a halogen atom (fluorine, chlorine, bromine atom, etc.), carbon Number 1 to 20 alkyl groups (methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl groups, etc.),
Aryl groups (phenyl, naphthyl groups, etc.), alkoxy groups (methoxy, ethoxy, butoxy, octyloxy, dodecyloxy groups, etc.), aryloxy groups (phenoxy,
2,4-di-t-amylphenoxy, 4- (4-dodecylphenylsulfonyl) phenoxy, naphthoxy group, etc.),
Alkylthio group (methylthio, ethylthio, butylthio group, etc.), arylthio group (phenylthio, naphthylthio group, etc.), alkylcarbonyl group (acetyl, propionyl, butyryl group, etc.), arylcarbonyl group (benzoyl, 4-methoxybenzoyl group, etc.), alkyl Sulfonamide group (methanesulfonamide, butanesulfonamide group, etc.), arylsulfonamide group (benzenesulfonamide, p-tolylsulfonamide group, etc.), alkylsulfamonyl group (ethylsulfamoyl, dimethylsulfamonyl group, etc.) ), Arylsulfamoyl group (phenylsulfamonyl group, etc.), acylamino group (acetamide, hexanamide, benzamide group, etc.), alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonyl group, ari Examples include a lesulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, a hydroxyl group, a carboxyl group, an amino group or a substituted amino group, a nitro group, a cyano group, and a heterocyclic group. .

The substituent represented by R ₁ is not particularly limited, but specifically, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group. , Sulfinyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, Examples thereof include sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

More specific examples of the above groups include Japanese Patent Application No. 61-113.
The groups described on page 7, line 13 to page 19, line 3 of the specification No. 371 can be mentioned.

Next, specific examples of the magenta coupler represented by the above general formula [II] are shown below, but the present invention is not limited thereto.

The magenta coupler according to the present invention can be synthesized by various synthetic methods, for example, US Pat. No. 3,725,067, Research Disclosure 12443.
It can be synthesized by referring to the method described in No.

A specific synthesis example is shown below.

Synthesis Example (Synthesis of Exemplified Coupler (2)) The reaction scheme is as follows.

Synthesis of Intermediate (I) 19.4 g of 1-benzylidenethiocarbonohydrazide and 35.3 g of 4-dodecylsulfonyl-2-methyl-butanoic acid chloride were added to 300 ml of ethyl acetate, and triethylamine was added.
15.0 g was added dropwise. After heating under reflux for 2 hours, triethylamine hydrochloride was removed by heating. The liquid was cooled, the precipitated crystals were taken, and recrystallized from ethanol to obtain 43.4 g of Intermediate (I).

Synthesis of Intermediate (II) 20.4 g of the above Intermediate (I) and 6.6 g of 50% hydroxylamine aqueous solution were added to 400 ml of ethanol and heated under reflux for 2 hours.
The reaction solution is cooled, the precipitated crystals are collected and the intermediate (I
I) 12.2 g was obtained.

Synthesis of Intermediate (III) 10.1 g of the above Intermediate (II) and ethyl-2-chloro-2-
5.5 g of (N, N-diethylaminocarbonyl) acetate,
And 3.0 g of triethylamine were added to 100 ml of acetonitrile, and the mixture was heated under reflux for 3 hours. Triethylamine hydrochloride was removed by heating, and the mother liquor was concentrated under reduced pressure and recrystallized from ethanol to obtain 11.8 g of intermediate (III).

Synthesis of intermediate (IV) 11.5 g of the above intermediate and 3.1 g of phosphorus oxychloride were added to 80 ml of toluene.
In addition to 0.1 ml of dimethylformamide, the mixture was heated under reflux for 4 hours, and the solvent was distilled off under reduced pressure. 80 ml of ethanol and 5 g of triethylamine were added to the residue, and the mixture was heated under reflux for 2 hours. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (ethyl acetate-hexane mixed solvent) to obtain 7.8 g of a candy-like intermediate (IV).

Synthesis of Intermediate (V) 7.5 g of the above intermediate (IV) was heated to reflux in a nitrogen atmosphere for 20 hours in 20 ml of dodecane. After insoluble matter was removed by heating, the mixture was cooled. The precipitated solid was separated and recrystallized from acetonitrile to obtain 4.6 g of intermediate (V).

Synthesis of intermediate (VI) 4.4 g of the above intermediate (V) was mixed with 25 ml of acetic acid, 12 ml of sulfuric acid and 1.
The mixture was added to 2 ml of the mixed solvent and heated under reflux for 1 hour. After pouring 50 ml of water into the reaction solution, it was neutralized with a 4N sodium hydroxide aqueous solution. Then, the mixture was extracted with 200 ml of ethyl acetate and concentrated under reduced pressure to obtain 3.8 g of intermediate (VI).

Other 1H-pyrazolo [5,1-c] -1,2,4-triazole nuclei themselves were synthesized according to the above synthesis example. There are various methods for introducing X other than chlorine atom, for example, Japanese Patent Publication No. 46-43947.
Reference was made to the synthesis examples described in JP-A-59-99437, JP-A-60-140241 and the like.

The amount of the magenta coupler of the present invention added to the color photographic light-sensitive material of the present invention is 1.5 × 10 ⁻³ to 1 mol of silver.
The range of 7.5 × 10 ^-1 mol is preferable, and 1 × 1 is more preferable.
It is in the range of 0 ^{-2 to} 5 x 10 ^-1 mol.

The color photographic light-sensitive material of the present invention is, for example, color negative and positive films, and color photographic paper.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, a silver halide emulsion layer containing a magenta, yellow and cyan coupler as a photographic coupler and a non-light-sensitive layer are usually provided on the support in an appropriate number of layers. And the layered structure is laminated in the order of layers, but the number of layers and the order of layers may be appropriately changed depending on the priority performance and the purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes, as a silver halide, a conventional halogenated silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and the like. Any of those used for silver emulsions can be used.

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

Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, a compound known as an antifoggant or stabilizer in the photographic industry can be added for the purpose of preventing fog during photographic processing and / or maintaining stable photographic performance.

In the coupler photographic light-sensitive material of the present invention, a color antifoggant, a dye image stabilizer, an anti-UV agent, an antistatic agent, a matting agent, a surfactant and the like which are commonly used in light-sensitive materials can be used.

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

The color photographic light-sensitive material according to the present invention may contain a color developing agent as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer, and may be processed with an alkaline activating bath.

The color photographic light-sensitive material of the present invention is subjected to bleaching treatment and definition treatment 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 stabilizing treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[Examples] Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

Example-1 Magenta couplers (1), (2), (4), (7), (13), (21), according to the present invention as shown in Table 1.
(24) and the comparative couplers 1 to 3 described below are taken in an amount of 0.1 mol per 1 mol of silver, and 1 times the amount of tricresyl phosphate and 3 times the amount of ethyl acetate of the coupler are added,
It was heated to 60 ° C and completely dissolved. This solution is 1200m in a 5% gelatin aqueous solution containing 120 ml of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
l was mixed with l and emulsified and dispersed by an ultrasonic disperser to obtain an emulsion.

Next, this dispersion was added to 4 kg of a green-sensitive silver iodobromide emulsion (containing 6 mol% of silver iodide), and a 2% solution of 1,2-bis (vinylsulfonyl) ethane (water: methanol = 1:
1) 120 ml was added, and the mixture was coated on the transparent undercoated polyester base and dried to prepare samples 1-1 to 1-10. (Coating silver amount 20 mg / 100 cm ² ).

The sample thus obtained was subjected to wedge exposure according to a conventional method and then subjected to the following development processing. The specific sensitivity, formalin resistance and light resistance of each sample will be described later in 1) to 3).
And the maximum concentration was measured.

(Development process) Color developer 38 ℃ 3 minutes 15 seconds Bleaching solution 38 ℃ 4 minutes 20 seconds Water washing 38 ℃ 3 minutes 15 seconds Fixing solution 38 ℃ 4 minutes 20 seconds Water washing 38 ℃ 3 minutes 15 seconds Stability Solution 38 ℃ 1 minute 30 seconds Dry 47 ℃ ± 5.5 ℃ 16 minutes 30 seconds The composition of the processing solution used in each processing step is as follows.

(Color developer composition) Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 5 g Sodium bromide 1.3 g Potassium iodide 2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g Sodium diethylenetriaminepentaacetate 2.5 g 4-Amino-3 -Methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulphate 4.8g Potassium hydroxide 1.2g Add water to make 1 and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Bleaching solution composition) Iron diamine tetraacetic acid ammonium salt 100 g Ethylene diamine tetraacetic acid 10 g Ammonium bromide 150 g Glacial acetic acid 40 ml Sodium bromate 10 g Add water to make pH 1 and use ammonia water or glacial acetic acid to adjust the pH to 3.5. Adjust to.

(Fixer composition) Ammonium thiosulfate 180 g Anhydrous sodium sulfite 12 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Sodium carbonate 10 g Water is added to make 1.

(Composition of stabilizing solution) Formalin (37% aqueous solution) 2 ml Conidax (Konishi Rokusha Kogyo KK) 5 ml Add water to make 1.

The measurement results are shown in Table 1. From Table 1, the sample using the coupler according to the present invention has not only high color development (that is, high specific sensitivity and maximum density comparable to that of the prior art) but also formalin resistance, and further excellent light resistance. I understood it.

* 1 The specific sensitivity is the reciprocal of the exposure dose that gives a density of fog +0.1. Sample No. 1-1 using the comparative coupler (1)
It was 100.

* 2 The sample is placed in a closed container containing 6 ml of a 0.9% formalin aqueous solution whose temperature and humidity have been adjusted to 30 ° C and 62% RH for 3 days, and then color development is performed. For comparison, a sample not treated with formalin is developed together. The formalin resistance was calculated according to the following formula.

* 3 The sample after color development was irradiated on a xenon fade meter for 5 days, and the residual dye% at the initial density = 0.1.
showed that.

Example-2 Samples 1-1 to 1-10 in Example-1 were subjected to wedge exposure in the same manner as in Example-1, and the following development processing was performed as the development processing. The results are shown in Table 2. The specific sensitivity and light resistance were measured by the same method as in Example-1.

(Development processing step) Color development 38 ° C 3 minutes 30 seconds Bleach fixing 33 ° C 1 minute 30 seconds Stabilization treatment / or water washing treatment 25-30 ° C 3 minutes Drying 75-80 ° C 2 minutes Treatment used in each processing step The liquid composition is as follows.

(Color developer) Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4-amino -N-Ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Set to 1 and adjust to pH 10.20.

(Bleach-fixing solution) ethylenediaminetetraacetic acid ferric ammonium dihydrate 60
g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 1.

(Stabilizing Solution) 5-Chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g As is clear from the results in Table 2, Samples 2-4-2 containing the coupler according to the present invention. It can be seen that -10 is superior in color developability (that is, has high specific sensitivity and maximum density comparable to that of the conventional sample) and is excellent in light resistance as compared with the comparative sample regardless of the development treatment.

Example 3 A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on a polyester resin-coated paper containing anatase type titanium oxide.

The following addition amounts are based on 100 cm ² .

(1) 20 mg gelatin, 5 mg silver-sensitive silver chlorobromide emulsion, and 8 mg yellow coupler and 0.1 mg 2,
A blue-sensitive emulsion layer containing 3 mg of dioctyl phthalate in which 5-di-t-octylhydroquinone was dissolved.

(2) 2 mg in which 12 mg of gelatin, 0.5 mg of 2,5-di-t-octylhydroquinone and 4 mg of an ultraviolet absorber were dissolved.
An intermediate layer containing dibutyl phthalate.

(3) 18 mg of gelatin, 4 mg of silver-sensitive green chlorobromide emulsion, and 5 mg of magenta coupler and 0.2 mg of 2.
A green-sensitive emulsion layer containing 2.5 mg of dioctyl phthalate in which 5-di-t-octylhydroquinone was dissolved.

(4) An intermediate layer containing the same composition as (2).

(5) 16 mg of gelatin, 4 mg of silver-sensitive silver halide chlorobromide emulsion, 3.5 mg of cyan coupler and 0.1 mg of 2.
A red-sensitive emulsion layer containing 2.0 mg of tricresyl phosphate in which 5-di-t-octylhydroquinone was dissolved.

(6) A gelatin protective layer containing 9 mg of gelatin.

A coating aid was added to each of the layers (1) to (6), and a hardening agent was added to each of the layers (4) and (6).

As the ultraviolet absorbers (2) and (4),
UV-1 and UV-2 were mixed and used.

The above-mentioned multilayer photosensitive material was processed in the same manner as in Example-2. The coupler is a yellow coupler (Y-1, Y-2),
Cyan couplers (C-1 to C-4), magenta couplers (1), (2) and (3) according to the present invention and Example-1.
Comparative coupler 1 used in 1. was used. Table 3 shows the sample configurations and test results.

Each sample was measured for magenta density after white exposure.

The specific sensitivity, maximum density, and light resistance were measured by the same methods as in Example-1.

It is clear from Table 3 that the coupler according to the present invention is excellent in light fastness of the dye image, and further improved by using the ultraviolet absorber.

UV absorber Y coupler C coupler [Effects of the Invention] As described above, the silver halide photographic light-sensitive material using the magenta coupler of the present invention has markedly improved light resistance and formalin resistance of a magenta color image, and has high color development.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one layer of the silver halide emulsion has the general formula [I].
A silver halide photographic light-sensitive material containing a magenta coupler represented by: General formula [I] (In the formula, Y ₁ and Y ₂ may be the same or different and each represents a hydrogen atom, an alkyl group or a cycloalkyl group, and Y ₁ and Y ₂ are not both hydrogen atoms. Also
Y ₁ and Y ₂ are bonded to each other with a nitrogen atom to form a 5-membered or 6-membered structure.
May form a heterocycle. R ₁ represents a hydrogen atom or a substituent. )