JPH0640215B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial 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.

[Conventional technology]

The coupler which has been conventionally put to practical use for forming a magenta dye is a pyrazolone type coupler, which has an unfavorable side absorption and is poor in storage stability, particularly resistance to formalin gas (formalin resistance). Have a point.

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 compound described in Research Disclosure No. 12443 cannot be put to practical use at all in terms of color forming property. 1H-pyrazolo [5,1-c] -1,2,4 described in JP-A-58-42045
-The triazole-type magenta couplers have been remarkably improved in terms of formalin resistance and color development, but also little improvement 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.

[Object of the Invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material having good light resistance and formalin resistance and high color development.

[Structure of Invention]

The above-mentioned object of the present invention is to provide 1H-pyrazolo [5,1-c] -1,2, in at least one silver halide emulsion layer having at least one silver halide emulsion layer on a support. The 6-position of a 4-triazole type magenta coupler is achieved by a silver halide photographic light-sensitive material containing a magenta coupler substituted with a substituent represented by the following general formula [I].

General formula [I] In the formula, Y represents an oxygen atom, a sulfur atom or SO ₂ , and R
₁ represents a substituent. n represents an integer of 0 to 5.

The 1H-pyrazolo [5,1-c] -1,2,4-triazole type magenta coupler of the present invention is represented by the following general formula [II].

General formula (II) In the general formula [II], R ₁ and n have the same meaning as in the general formula [I], and R ₂ represents a hydrogen atom or a substituent.

X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a color developing agent.

The substituent R ₁ on the benzene ring of the general formula [I] is not particularly limited, but preferably a halogen atom (fluorine, chlorine,
Bromine atom, etc.), alkyl group having 1 to 20 carbon atoms (methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl group, etc.), aryl group (phenyl, naphthyl group, 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.), alkylsulfonamide group (methanesulfonamide, butanesulfonamide group, etc.), arylsulfonamide group (benzenesulfonamide, p-tolylsulfonamide group, etc.), alkylsulfamoyl group ( Ethylsulfamoyl, dimethylsulfamoyl group, etc.), arylsulfamoyl group (phenylsulfamoyl group, etc.), acylamino group (acetamide, hexanamide, benzamide group, etc.), alkylcarbamoy Group, arylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylcarbonyloxy group, arylcarbonyloxy group, hydroxyl group, carboxyl group, amino group or substituted amino group, nitro group, cyano group And a heterocyclic group.

The substituent represented by R ₂ 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.

The group capable of splitting off by the coupling reaction with the oxidation product of the color developing agent represented by X is a halogen atom (eg, fluorine, chlorine, bromine atom, etc.), an amino group, a substituted amino group (eg, acylamino, diacylamino, alkylamino). , Arylamino groups, etc.), azo groups, aryloxy groups (eg phenoxy, p-methoxyphenoxy, p-butanesulfonamidophenoxy, p-carboxyphenoxy groups etc.), alkoxy groups (eg methoxy, ethoxy, 2-methoxyethoxy groups). Etc.), arylthio group (eg phenylthio, p-carboxyphenylthio group etc.), alkylthio group (eg methylthio, 2-hydroxyethylthio group etc.), heterocyclic thio group (eg 1-ethyltetrazole-5-thioyl, 2- Pyridylthio group, etc.), heterocyclic group (eg 1-pyrazoli , 1-imidazolyl, 2,5 Pirazorinjion-1-yl group etc.), a carboxyl group, a sulfo group, an alkoxycarbonyl group, an aryloxycarbonyl group, and the like aralkyloxycarbonyl groups.

Among the groups represented by X, a halogen atom is preferable, and a chlorine atom is particularly preferable.

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 according to various synthetic methods, for example, the method described in JP-B-46-43947.

A specific synthesis example is shown below.

Synthesis Example (Synthesis of Exemplified Coupler (1)) The reaction scheme is as follows.

Synthesis of Intermediate (I) 29 g of methyl acetoacetate and 28% sodium methoxide
53 g of a methanol solution was added to 150 ml of toluene, and methanol was distilled off while heating under reflux. Next, a solution prepared by dissolving 78 g of 2,5-di-t-pentylphenoxyacetic acid chloride in 50 ml of toluene was added dropwise. After heating under reflux for 5 hours, 53 g of 28% sodium methoxide / methanol solution was added, and the temperature was 60 ° C.
And reacted for 2 hours. 65 ml of hydrochloric acid and 500 ml of water were added to the reaction solution, the organic solvent layer was separated, the organic solvent was distilled under reduced pressure, and the residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate-hexane to obtain an oily intermediate (I). 2
3.9 g was obtained.

Synthesis of Intermediate (II) 23 g of the above Intermediate (I) was dissolved in 150 ml of chloroform, and 9.
After 36 g of sulfuryl chloride was added dropwise, the mixture was stirred at room temperature for 30 minutes. Chloroform was distilled off under reduced pressure, and α-chloro-α- (2,
24.5 g of methyl 5-di-t-pentylphenoxy) acetate was obtained.

1-benzylidenethiocarbohydrazide (12.8 g) was suspended in 200 ml of ethanol containing 4.7N hydrochloric acid to prepare a solution of α-chloro-α.
Methyl-(2,5-di-t-pentylphenoxy) acetate 24.
After dropwise adding 5 g, the mixture was heated under reflux for 1.5 hours. After cooling, the precipitated crystals were collected by filtration to obtain 22 g of intermediate (II). Melting point 219 ~
223 ° C.

Synthesis of Intermediate (III) 14.7 g of the above Intermediate (II) was suspended in 500 ml of ethanol, and
% Hydroxylamine aqueous solution 4.1g, potassium hydroxide
A solution prepared by dissolving 0.78 g in 5 ml of water was added, and the mixture was heated under reflux for 2 hours. Water (500 ml) and sodium hydroxide (0.50 g) were added to the reaction solution, and the precipitated crystals were collected by filtration to obtain 10.9 g of intermediate (III). Melting point 182-184 ° C.

Synthesis of Intermediate (IV) To 10.8 g of the above Intermediate (III) and 200 ml of ethyl acetate, 6.7 g of myristin chloride and 4.0 g of triethylamine were sequentially added. After stirring at room temperature for 1 hour, the precipitated triethylamine hydrochloride was filtered off and the mother liquor was concentrated to give an oily intermediate (I
V) 15.3g was obtained.

Synthesis of intermediate (V) 15.2 g of the above intermediate (IV) and 5.0 g of oxychloride were added to toluene 2
It was added to 00 ml and heated under reflux for 1 hour. Toluene was distilled off under reduced pressure, 200 ml of acetonitrile and 8.0 g of pyridine were added, and 1 more was added.
Heated to reflux for hours. The reaction solution is filtered while hot, and the filtrate is concentrated and then subjected to silica gel column chromatography (ethyl acetate-
Purification with a hexane mixed solvent) gave 7.6 g of intermediate (V). Melting point 66-67 ° C.

Synthesis of Intermediate (VI) 6.5 g of the above Intermediate (V) was added to 50 ml of acetic acid, 12.5 ml of sulfuric acid and water.
The mixture was added to 2.5 ml of mixed solvent and heated at 60 ° C for 1 hour. The reaction mixture was neutralized with aqueous sodium hydroxide solution, extracted with ethyl acetate, concentrated under reduced pressure, and purified by silica gel column chromatography using a mixed solvent of ethyl acetate-hexane. 3.4 g of intermediate (VI) having a melting point of 104-105 ° C was obtained.

Synthesis of Exemplified Coupler (1) 1.6 g of intermediate (VI) was dissolved in 50 ml of chloroform, and 0.40 g of N-chlorosuccinimide (NCS) was added little by little. After stirring at room temperature for 1 hour, chloroform was distilled off under reduced pressure, ethyl acetate and water were added, and the organic solvent layer was separated. After the solvent was concentrated, the residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate-hexane to obtain 1.7 g of pale yellow wax-like exemplary coupler (1).

Elemental analysis value (C ₃₄ H ₅₅ ClN ₄ O) Calculated value (%) C: 71.48 H: 9.70 N: 9.81 Cl: 6.21 Measured value (%) C: 71.71 H: 9.95 N: 10.02 Cl: 6.5
5 FD-mass spectrum shows M ⁺ 570 as parent peak,
It was supported that this compound has the structure of the target exemplary coupler (1).

Other 1H-pyrazolo [5,1-c] -1,2,4-excluding the leaving group X
The triazole nucleus itself was synthesized according to the above synthesis example. There are various methods for introducing X other than a chlorine atom, such as JP-B-46-43947, JP-A-59-99437, and JP-A-60-14024.
The synthesis examples described in No. 1 etc. were referred to.

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 color photographic light-sensitive material of the present invention, an anti-foggant, a dye image stabilizer, an anti-UV agent, an antistatic agent, a matting agent, a surfactant and the like which are usually 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 can contain a color developing agent as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer, and can be processed with an alkaline activating bath.

The color photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing 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.

〔Example〕

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

Example-1 Magenta coupler (1) according to the present invention as shown in Table 1,
0.1 mol of (4), (8), (11), (15), (16), (21) and comparative couplers 1 to 3 described later were taken for each 1 mol of silver, and the amount was 1 time the coupler weight. Of tricresyl phosphate and 3 volumes of ethyl acetate were added, and the mixture was heated to 60 ° C. and completely dissolved. This solution was mixed with 1200 ml of a 5% gelatin aqueous solution containing 120 ml of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and emulsion-dispersed with 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 as a hardening agent (water: methanol =
1: 1) 120 ml was added, and it was coated and dried on the transparent undercoated polyester base to prepare samples 1-1 to 1-10. (Amount of coated silver: 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 Stabilization 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 30g Sodium hydrogencarbonate 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g Sodium diethylenetriaminepentaacetate 2.5g 4-Amino-3-methyl- N-Ethyl-N- (β-hydroxyethyl) aniline sulfate 4.8 g Potassium hydroxide 1.2 g Water is added to make 1 and the pH is adjusted to 10.06 with potassium hydroxide or 20% sulfuric acid.

(Bleaching solution composition) Iron diamine tetraacetate ammonium salt 100 g Ethylene diamine tetraacetic acid 10 g Ammonium bromide 150 g Glacial acetic acid 40 ml Sodium bromate 10 g Water is added to adjust to pH 3.5 using ammonia water or glacial acetic acid.

(Fixing solution 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. It can be seen from Table 1 that the sample using the coupler according to the present invention has high color developability (that is, high specific sensitivity and comparable maximum density), and excellent formalin resistance and light resistance.

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. The results are shown in Table 2. The specific sensitivity and light resistance were measured by the same method as in Example-1.

(Development process) Color development 38 ° C 3 minutes 30 seconds Bleach fixing 33 ° C 1 minute 30 seconds Stabilization / 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 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N -Ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to make the total amount 1 Adjust to pH 10.20.

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

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one
1.0 g ethylene glycol 10 g As is clear from the results shown in Table 2, Samples 2-4 to 2-10 containing the coupler according to the present invention are superior in color developability to the comparative sample (that is, high specific sensitivity and maximum density). It is comparable to the conventional one), and it has excellent light resistance.

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

The following addition amounts are based on 100 cm ² .

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

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

(3) 18 mg gelatin, 4 mg green sensitive silver chlorobromide emulsion, and 5 mg magenta coupler and 0.2 mg 2,5-
A green-sensitive emulsion layer containing 2.5 mg of dioctyl phthalate in which 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 chlorobromide emulsion, and 3.5 mg of cyan coupler and 0.1 mg of 2,5-
A red-sensitive emulsion layer containing 2.0 mg of tricresyl phosphate in which di-t-octylhydroquinone was dissolved.

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

A coating aid is added to each layer of (1) to (6), and (4) and
A hardener was added to the layer (6).

Examples of the ultraviolet absorbers (2) and (4) include UV-absorbers having a structure described later.
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 comparative coupler 1 used in Example 1 were used. Sample configuration and test results
The results are shown in Table 3.

Each sample was measured for magenta density after white exposure.

Further, the comparison, the maximum density, and the light resistance were measured in the same manner 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.

[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 1H-pyrazolo [5,1-c] is provided in at least one of the silver halide emulsion layers. A silver halide photographic light-sensitive material characterized in that it contains a magenta coupler in which the 6-position of the 1,2,4-triazole type magenta coupler is substituted with a substituent represented by the following general formula [I]. General formula [I] [In the formula, Y represents an oxygen atom, a sulfur atom, or SO ₂ ,
R ₁ represents a substituent. n represents an integer of 0 to 5. ]