JPH0466018B2 - - Google Patents

Description

[Detailed description of the invention]

1. BACKGROUND OF THE INVENTION Technical Field The present invention relates to a silver halide photographic material containing a novel magenta dye-forming coupler. Prior art and its problems As is well known, in subtractive color photography, aromatic
A grade amine color developing agent oxidatively couples the oxidation products of the color developing agent produced by reducing exposed silver halide grains with couplers that form yellow, cyan, and magenta dyes in a silver halide emulsion. A dye image is thereby formed. In these cases, as a yellow coupler for forming a yellow dye, a compound having an open-chain active methylene group is generally used, and as a magenta coupler for forming a magenta dye, a pyrazolone type, pyrazolinobenzimidazole type, Compounds such as indazolone-based compounds are used, and compounds having phenol and naphtholic hydroxyl groups are used as cyan couplers to form cyan dyes. Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent if necessary, and added to the silver halide emulsion, or dissolved in an aqueous alkaline solution. Added to silver halide emulsions. The former is an oil droplet dispersion method;
The latter is an alkali dispersion method, and the former is generally considered to be superior to the latter in terms of light resistance, heat resistance, moisture resistance, color sharpness, etc. The basic properties required for each coupler are:
In addition to simply forming dyes, the dyes must first have high solubility in high-boiling organic solvents or alkalis, and have good dispersibility and stability in silver halide photographic emulsions. , have fastness against heat and moisture, etc., have good spectral absorption characteristics, have good transparency, have high color density, and have excellent sharpness and graininess of the resulting image. It is desired to have various characteristics such as the ability to However, to the best of the knowledge of the present inventors, no conventionally known magenta coupler has yet been found that satisfies all of the above-mentioned required properties. Various pyrazolone derivatives are known as magenta couplers, but these couplers have low coloring efficiency, and in so-called four-equivalent couplers in which the coupling active position is unsubstituted, the proportion of coupler used for dye formation is about half, The rest is not useful for pigment formation. As a method for improving the color development efficiency, a so-called two-equivalent magenta coupler is known in which a substituent (leaving group) capable of splitting off during color development is introduced into the active position of a pyrazolone derivative. Examples of these two-equivalent magenta couplers include couplers having an acyloxy group as a leaving group in US Pat. No. 3,311,476, couplers having an aryloxy group in US Pat. No. 3,419,391, and couplers having a thiocyano group in US Pat. No. and same
No. 3,253,924, a coupler having a 2-triazolyl group is described in US Pat. No. 3,617,291, and a coupler having an acylthio group or a thioacylthio group is described in US Pat. No. 4,032,346. However, when these two-equivalent magenta couplers are used, they cause significant color fogging, have low coupling activity, or are chemically unstable and cannot develop color over time. However, it has been accompanied by some disadvantages, such as a change in the composition, and furthermore, there are many difficulties in synthesis. Previously, U.S. Patent No. 3,227,554 and
As disclosed in No. 3701783, compounds in which the active position 4 of a pyrazolone derivative was substituted with an arylthio group or a heterocyclic thio group were also known. However, many of these known thio-substituted pyrazolone compounds are so-called development inhibitor-releasing couplers (DIR couplers), in which the mercaptan produced as a result of the coupling reaction interacts with silver halide and has the function of delaying development. It was hot. In order to prevent the strong photographic effects of mercaptans, a thio-substituted pyrazolone coupler having a mercaptan compound with a diffusion-resistant group as a leaving group was developed by Tokko Sho.
No. 53-34044, JP-A-54-80744 and JP-A-57
However, these couplers do not have sufficient coupling activity and there are problems with the storage stability of the magenta dyes produced, making it difficult to apply them to general color photographic materials. Furthermore, JP-A-55-62454 describes a magenta coupler in which the 4-position of a pyrazolone derivative is substituted with R'-S- (R' represents a straight or branched alkyl or aralkyl). In these couplers, the mercaptan compound that is released after coupling does not have a substantial development-inhibiting effect; however, the coupling activity of the couplers is low, and image storage stability, especially light resistance, is poor. It had drawbacks. Furthermore, in JP-A No. 55-29805, the 4-position of pyrazolone derivatives is

【formula】(

[Processing process (38℃)]

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixation 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds [Color developer composition] 4-Amino-3-methyl- N-ethyl-N-(β
-hydroxyethyl)-aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and use potassium hydroxide to adjust the pH.
Adjust to 10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to 1 and use ammonia water to make pH6.0
Adjust to. [Fixer composition] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH6.0 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. The magenta dye image obtained above was measured with green light using a densitometer (PD-7R Konishiroku Photo Industry Co., Ltd.), and the color development sensitivity (relative value when the sensitivity of sample (11) was set to 100) was measured. ), fog and maximum density were calculated and the results are shown in Table 1 below.

[Table] From the results shown in Table 1 above, samples (1), (2), (3) and (4) using the couplers of the present invention are superior to samples (5) to (11) using the comparative couplers. It was found that it has higher coloring sensitivity and highest sensitivity than that, and also shows improved coloring performance with no increase in capri. Example 2 After coating the samples (1) to (11) prepared in Example 1, they were placed in a sealed container containing 1% formaldehyde aqueous solution in a dark room without exposure to light for 3 minutes without touching the solution. I left it for days. These samples and an untreated sample for comparison were exposed and developed in the same manner as in Example 1, sensitivity and maximum density were measured, and formalin resistance % (treated sample/untreated sample x 100) was calculated. The results obtained are shown in Table 2.

【table】

[Table] From the results shown in Table 2, samples (1) to (4) using the coupler of the present invention are different from sample (5) using the comparative coupler.
-(11), it can be seen that this coupler is less susceptible to adverse effects such as a decrease in sensitivity and a decrease in maximum concentration due to formalin and has excellent properties in preserving raw samples. Example 3 A durability test was conducted using the dye image samples (1) to (11) prepared in Example 1. That is, as a durability test, the above sample was left for two weeks at 40% RH and 80°C. In addition, as a light resistance test, the sample was treated with a xenon fade meter (6KW) for 100 hours. Also, as a humidity resistance test, 60℃, 80%
The samples were left at RH for 4 weeks. These samples were measured under green light and the percent dye remaining was calculated. Here, the dye remaining % is the dye concentration before the durability test.
The density after the durability test in the exposed area showing 1.0 is expressed as a percentage. Regarding heat resistance and light resistance, the portion with a density of 1.0 was simultaneously measured using blue light, and the yellow contamination percentage (density after durability test/density before durability test x 100) was calculated. The results obtained are shown in Table 3.

【table】

[Table] From the results shown in Table 3, samples (1), (2), (3) and (4) using the couplers of the present invention are different from samples (5) to (11) using the comparative couplers. It can be seen that the coupler according to the present invention is an excellent coupler that is stable in terms of durability and does not easily cause a decrease in image density even during storage, since the occurrence of yellow stain is less than that of the coupler of the present invention. Example 4 Exemplary couplers (6), (9), (12), (18) and comparative couplers (H), (I) were each dissolved in 5 x 10 ^-3 moles of 4 ml of tricresyl phosphate and 12 ml of ethyl acetate. The mixture was heated and dissolved, and this solution was mixed with 70 ml of a 5% latin aqueous solution containing 1.5 g of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont), and emulsified and dispersed using a colloid mill. 1 kg of photographic emulsion containing 0.2 mol of green-sensitive silver iodobromide (silver iodide 6 mol%, silver bromide 94 mol%) and 30 g gelatin was prepared using a dispersion of this coupler.
20 ml of a 2% solution of 1,2-bis(vinylsulfonyl)ethane was added as a hardening agent, and the mixture was coated on a cellulose triacetate film base and dried.
A gelatin protective layer was applied on top of this layer to prepare silver halide color photographic materials samples (12) to (17). The silver coating material for each sample at this time was 1 g/m ² . These samples were each subjected to wedge exposure in a conventional manner and then subjected to the same treatment using the treatment solution used in Example 1. The magenta dye image obtained by this process was measured with green light using a densitometer (RD-7R manufactured by Konishiroku Photo Industry Co., Ltd.),
The color density was determined. The color density was expressed as a relative value, with the color density in sample (16) being 100. In addition, using a microdensitometer (PDM-5, manufactured by Konishiroku Photo Industry Co., Ltd.), we scanned the areas with densities of 0.3 and 0.6 with a scanning aperture of 5 x 50μ, and measured the RMS granularity at that time using the "Chemistry of Photography". (Shashin Kogyo Publishing), pp. 420-425, 1982, etc., the relative granularity was calculated when sample (16) was taken as 100, and the results are shown in Table 4. .

[Table] As is clear from Table 4, samples (12) to (15) using the magenta coupler of the present invention have higher color development sensitivity than samples (16) and (17) using the comparative coupler. The results show that the magenta coupler of the present invention has high sensitivity and also shows good relative granularity (the smaller the value, the better).

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer provided on a support, a magenta coupler represented by the following general formula [I] is provided in the silver halide emulsion layer. A silver halide photographic material containing at least one kind of. General formula [I] (In the formula, R ₁ is an alkyl group, an aryl group, or
It represents a heterocyclic group, R ₂ and R ₃ each represent an alkyl group, and Ar represents an aryl group. )