JPS6310812B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide color photographic light-sensitive material containing a photographic coupler having a novel function. Conventionally, photochemically useful performance and functions have been imparted by introducing various substituents into the coupler at positions that can react with the oxidized form of the color developing agent (hereinafter referred to as active sites). things have been done. For example, by using a so-called 2-equivalent coupler, which has a group that easily detaches from the active site and has no effect on photochemistry, the coupling property can be improved and the amount of silver required to obtain a dye image can be reduced by 1/2. 2, and as a result, the emulsion layer can be made thinner, improving sharpness. Also, so-called colored couplers, in which dyes are bound to active sites, can perform color correction of dye photographic images. Furthermore, the so-called DIR coupler, in which a development inhibitor is bound to the active site, has functions such as controlling image tone, making the dye image finer, and interlayer effect.
Naturally, attempts have also been made to attach other photochemically useful substituents to the active site. Looking at the trends in color photography over the past 10 years, there are two trends that stand out.
One is the shift to smaller film sizes, and the other is higher sensitivity. In other words, the former is a transition from 135 size to 110 size, and the latter is a transition from ASA sensitivity 50 to ASA sensitivity 100.
This is a transition to ASA sensitivity 400. Reducing the film size not only saves silver resources, which are becoming depleted, but also allows cameras to be made smaller, providing easy-to-use and portable cameras, so-called pocket cameras. High sensitivity increases productivity per unit time for color photographic paper, providing cheaper color prints, and for color film, it increases the productivity per unit time.
It has become possible to take photographs even in dark places without using auxiliary light sources such as flash or strobe lights. However, the 110 size film still does not have sufficient graininess, color reproducibility, sharpness, etc., and therefore cannot meet the demand for smaller film sizes. Also
When using a film with an ASA sensitivity of 400, the image quality is inferior to that of a film with an ASA sensitivity of 100 due to the basic property of silver halide photography that the higher the sensitivity, the larger the silver halide grains become. It is an undeniable fact that it does. Various methods have been devised in the past to improve these drawbacks. The above-mentioned DIR couplers and colored couplers are one such method, and other methods include thinning the photosensitive emulsion layer, separating the photosensitive layer in the same wavelength range into a high-density silver halide layer and a low-density silver halide layer, These include improvements in silver halide manufacturing technology, anti-halation technology, anti-irradiation technology, and coupler improvements. However, it is still insufficient, and further improvement is desired. SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic material having graininess and color reproducibility sufficient to meet the demands for smaller film sizes by using couplers with new functions. The object of the present invention is to provide a non-diffusive coupling component capable of coupling with an oxidized form of a color developing agent, and a halogen containing photographic coupler having a diffusible substituent bonded at a position capable of being substituted by the coupling. In a silver oxide color photographic light-sensitive material, the diffusible substituent is released from the coupling component to couple with the oxidized product of the color developing agent as a 4-equivalent coupler to form a dye. This can be achieved using a silver halide color photographic material characterized by being combined with a coupling component. A preferred photographic coupler of the present invention is represented by the following general formula []. Complete set [] In the formula, non-diffusion type COUP (A) represents a non-diffusion type coupling component (A), and diffusion type COUP (B) represents a diffusion type coupling component (B). However, non-diffusive COUP (A) combines with the oxygen atom O at a position where it couples with the oxidized form of the color developing agent to form a colored or colorless compound, and diffusive COUP (B) forms a non-diffusive COUP ( When A) is coupled, it is released and forms a non-diffusive COUP (A) through an oxygen atom in a form that can couple with an oxidized color developing agent to form a dye as a 4-equivalent coupler. are combined. Although the mechanism of action by which the compound represented by the general formula [] of the present invention significantly improves graininess and sharpness has not been fully elucidated, it is presumed to be roughly as follows. Generally, one of the causes of deterioration in graininess is when a large amount of coloring dye is produced in a short period of time when a coupler couples with an oxidized product of a color developing agent. Therefore, it is common that couplers with faster coupling have worse graininess. In such a case, the compound of the general formula [] is used as the color developing agent generated in large quantities by the coupling of the oxidized color developing agent and the diffusive COUP (B), and the dye generated in large quantities flowing out of the system. effectively removes some of the oxidants of In addition, to improve color reproducibility, a part of the diffusive COUP (B) imagewise split off from the coupler of the general formula [] diffuses into the adjacent layer, where it removes the oxidized form of the color developing dye. This is presumed to be due to the interlayer effect. The non-diffusive coupling component (A) of the present invention and the coupling component (B) used for the diffusive substituent are selected from the residues of yellow, cyan, and magenta couplers that are normally used in silver halide photographic light-sensitive materials. be able to. Some of these couple with the oxidized form of a color developing agent to form a colorless compound, while others form a colored compound. The terms "non-diffusive type" and "diffusable type" are commonly used by those skilled in the art, and are distinguished depending on whether or not they have a diffusion-inhibiting group (Ballast group). Regarding the yellow coupler, U.S. Patent No.
No. 298443, No. 2407210, No. 2875057, No.
3048194, 3265506, 3447928, and "Farbkuppler eine
There are benzoylacetanilide-type yellow couplers and pivaloylacetanilide-type yellow couplers, which are described in Agfa Mitairnig (vol.), pp. 112-126 (1961). Regarding magenta couplers, US Patent No. 2369489, US Patent No. 2343703, US Patent No. 2311082,
Same No. 2600788, Same No. 2908573, Same No. 3062653,
There are various magenta couplers such as pyrazolone magenta couplers and indazolone magenta couplers, which are described in the specifications of 3152896 and 3519429, and in the above-mentioned Agfa Mitteilung (Band) pages 126-156 (1961). . Furthermore, as a cyan coupler, U.S. Patent No.
No. 2367531, No. 2423730, No. 2474293, No. 2772162, No. 2895826, No. 3002836,
No. 3034892, No. 3041236 and the Agfa Mitteilung (Band) pages 156-175 (1961
There are naphthol-based or phenolic couplers listed in 2010). Next, typical examples of the compounds of the present invention will be listed, but the present invention is not limited thereto. Below, methods for synthesizing representative examples of the compounds of the present invention are shown. Synthesis example Synthesis of exemplified compound-2 Dissolve 2.15g of () in 30ml of dry DMF,
Gradually add 0.5 g of NaH while stirring. After the foaming subsides, add 6.0 g of () and stir at room temperature for 8 hours. Pour this reaction solution into diluted hydrochloric acid water and collect the resulting crystals. After air drying, the white crystals were dissolved in a small amount of benzene, and the desired phase was separated by silica gel chromatography using benzene-ethyl succinate as a developing solution. 2.8g of yellow syrup was obtained. Confirmed by mass spectrum NMR. Synthesis of Exemplified Compound-6 6 g of (), 2.4 g of () and 2 g of anhydrous potassium carbonate were stirred in 50 ml of ethyl acetate at room temperature for 8 hours. The reaction solution was filtered and the solution was concentrated under reduced pressure to obtain a pale yellow candy-like compound (). Dissolve this in 50 ml of methanol and stir to remove 3 g.
Gradually add a solution of KOH dissolved in 5 ml of water. Stir at room temperature for 3 hours. The reaction solution was poured into diluted hydrochloric acid water, and the resulting crystals were collected. After air drying, recrystallize with methanol, 4.8
A pale white crystal of g was obtained. Confirmed by mass spectrum NMR at mp120-125°C. Compounds similar to the compounds of the present invention are described in JP-A-52-150631, but these compounds have a 4-alkyl-substituted-5-pyrazolone bonded to the active site of a yellow coupler. Not only is the coupling with the oxidized form of the color developing agent not only insufficient, but also the 4-alkyl-substituted-5-pyrazolone is a 2-equivalent coupler even if it is released from the active site. Only half of the compound, the oxidized form of the developing agent, can be removed. For the above-mentioned presumed reasons, when the compound of JP-A-52-150631 was used in a high-sensitivity silver halide emulsion, it did not exhibit the same function as the compound of the present invention.
Therefore, it is a surprising and unexpected fact that the compound of the present invention, such as Compound-6, which has almost the same structure as the compound of JP-A-Sho, greatly improves graininess and color reproducibility. That's what happened. Furthermore, British Patent No. 1546837 describes a compound in which the active sites of both a non-diffusive coupler and a diffusive coupler are bonded with a methylene group, but these compounds were tested using a highly sensitive halogenated emulsion. As a result, almost no improvement in graininess or color reproducibility was observed. The reason for this is that the active site of the compound described in the UK patent is a carbon-carbon bond, so the coupling reaction with the oxidized form of the color developing agent or the subsequent split-off is slow; It is thought that it is difficult to selectively specify the order of coupling because there are two of them. However, since the active site of the compound represented by the general formula () of the present invention is replaced by an oxygen bond, coupling is fast, the order can be easily defined, and synthesis is also easy. Also Research
Disclosure July 1980 No. 19536 and the same magazine 1980
August No. 19633 discloses that a diffusive coupler is used in place of the non-diffusive COUP (A) and a non-diffusive coupler is used in place of the diffusive COUP (B) of the compound represented by the general formula [] of the present invention. Compounds bonded to each other are described. Testing of these compounds showed significant improvement in graininess, but a decrease in sensitivity. The reason for this is that the color developing agent itself is oxidized by reducing the exposed silver halide, and the color developing agent that is coupled with the oxidized color developing agent generated in this process is diffused. This is due to the fact that it leaks out of the film system. In other words, the oxidized product of the color developing agent in the initial stage of development, which has a great effect on sensitivity, is wasted, resulting in a decrease in sensitivity. In contrast, the compound of the present invention does not cause a decrease in sensitivity by effectively utilizing the oxidized product of the color developing agent produced in the initial stage of development. On the contrary, since the diffusive COUP(B) in the general formula [] is of the diffusive type, it not only improves graininess, but also brings about the surprising phenomenon of further improving color reproducibility. I forced him to do so. Such functionality is described above.
This was not observed in the couplers described in the Research Disclosure, and could not even be predicted. The reason for this improvement in color reproducibility is presumed to be as follows. In other words, the compound of the present invention in which COUP (B) is a diffusive coupler in the general formula This is presumed to be due to a phenomenon called the so-called interlayer effect, in which COUP(B) diffuses into the adjacent layer and couples there with the oxidized form of the color developing agent present in the adjacent layer. Moreover, the produced dye flows out of the system, which is convenient. British Patent No. 1077874, U.S. Patent No. 3476563 and U.S. Patent No. 3644498 disclose couplers having an aryl group via an oxygen atom at the active site of the coupler.
Since the -O-aryl group released by coupling with the oxidized form of the color developing agent is a coupler that does not substantially couple with the oxidized form of the color developing agent, it does not have the function as the compound of the present invention. Not only is this not true, but the effects of the present invention cannot be expected at all. Although the coupler of the present invention can be used as it is in a silver halide color photographic light-sensitive material instead of a conventional coupler, it is preferable to use the coupler of the present invention in place of a part of the coupler. The compounds of the present invention can be dispersed in silver halide photosensitive materials by methods well known to those skilled in the art, and the optimum amount to be added can be easily determined by simple preliminary tests. The color developing agent of the present invention can be selected from those conventionally known in the art. Other various commonly used additives can be used in the silver halide color photographic material of the present invention. The silver halide color photographic material of the present invention includes:
a support; a red-sensitive silver halide emulsion unit in combination with a cyan dye image-forming material applied to the support; a green-sensitive silver halide emulsion unit in combination with a magenta dye image-forming material; and a yellow dye image. and blue-sensitive silver halide emulsion units in combination with forming materials, further comprising:
Each can consist of one or more layers. Also, the various units and layers can be arranged at different locations from each other. Embodiments suitable for the present invention are shown below with specific examples, but the present invention is not limited thereto. Example 1 α-pivaloyl-α-(2,5-dioxo-3,4-diphenylimidazolidine-1) was deposited on a subbed cellulose triacetate film support.
-yl)-2-chloro-5-[γ-(2,4-di-
10.7 g of tert-amylphenoxy)butyramide]acetanilide and 11 ml of tricresyl phosphate.
was dissolved in 30 ml of ethyl acetate, mixed with 20 ml of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 ml of a 5% aqueous gelatin solution, and emulsified and dispersed in a colloid mill.
An emulsion was obtained. This dispersion was added to 1 kg of a high-sensitivity silver iodobromide emulsion (containing 7 mol % silver iodobromide), and 40 ml of a 2% aqueous solution of 1,2-bis(vinylsulfonyl)ethane was added as a hardening agent for coating. (Coated silver amount 12
mg/100cm ² , coupler mole/Ag mole = 0.05). The obtained silver halide color light-sensitive material is referred to as Sample 1. Next, samples 2, 3 and 4 were obtained by adding coupler compound-2, compound-5 and compound-6 of the present invention in place of 1/3 of the coupler in sample 1. Similarly, Comparative Samples 1 and 2 were obtained by adding the following comparative couplers in place of 1/3 of the coupler in Sample 1. Comparison coupler 1 Compound comparison coupler 2 described in JP-A-52-150631 Compound described in British Patent No. 1546837 Each of these samples was exposed to light using an intensity scale sensitometer, and then subjected to color development according to the following processing steps. [Processing process] (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 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 In each processing step The composition of the treatment liquid used was as follows. [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxyamine 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 to PH10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Ice Vinegar Acid 10.0ml Add water to make 1, then adjust the pH using aqueous ammonia.
Adjust to 6.0. [Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162ml Anhydrous sodium sulfite 12.4g Add water to make 1, and adjust to PH6.5 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Table 1 shows the results of the samples developed in this manner. Sensitivity is the relative sensitivity value when sample 1 is taken as 100, and granularity is the value 1000 times the standard deviation of the variation in density value when the dye image is scanned with a microdensitometer with a circular scanning aperture of 25μ. represents.

[Table] From Table 1, the compounds of the present invention can reduce fog without decreasing sensitivity, keep gamma values low, and, compared to comparative couplers 1 and 2, improve graininess and increase maximum color density. It is clear that it is an excellent coupler in these respects as well. Example 2 α-hybaroyl-α-(2,5-dioxy-3,4-diphenylimidazolidine-1 of Example 1)
-yl)-2-chloro-5-[γ-(2,4-di-
1-Hydroxy-N-[4-
(2,4-di-tert-amylphenoxy)butyl]
Sample 1 using 10.6g of -2-naphthamide
shall be. Next, samples 2 and 3 were prepared by replacing 10% of the coupler in sample 1 with compound-7 and compound-8, which are couplers of the present invention. Similarly, a sample using 10% of the following comparative coupler was designated as Comparative Sample-1. Coupler described in Research Disclosure No. 19633 Each of these samples was exposed in the same manner as in Example 1.
After processing, the following Table 2 was obtained.

[Table] As can be seen from Table 2, the compound of the present invention has a large effect of improving graininess, and although the comparative sample has a decrease in sensitivity, the decrease in sensitivity is small. Example 3 Multilayer coatings were carried out on a transparent triacetate base in the following order. 1st layer: red-sensitive emulsion layer As a cyan coupler, 1-hydroxy-N-
10.6 g of [4-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide was dissolved in 11 ml of tricresyl phosphate and 30 ml of ethyl acetate, and this was dissolved in Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont). The mixture was mixed with 20 ml of a 10% aqueous solution and 200 ml of a 5% gelatin aqueous solution and emulsified and dispersed in a colloid mill to obtain an emulsion (). Thereafter, this dispersion was added to 1 kg of red-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), and 1,2-
40 ml of a 2% solution of bis-(vinylsulfonyl)ethane (water:methanol 1:1) was added and coated and dried. (Amount of coated silver: 20 mg/dm ² ) 2nd layer: Intermediate layer A gelatin intermediate layer containing 0.5 g/m ² of gelatin and 0.1 g/m ² of 2,5-di-tert-octylhydroquinone. 3rd layer: Green-sensitive emulsion layer 1-(2,4,6-
trichlorophenyl)-3-[3-(2,4-di-
tert-amylphenoxyacetamido)benzamide]-5-pyrazolone (15 g) was dissolved in 15 g of tricresyl phosphate and 45 ml of ethyl acetate, and an emulsion was prepared in the same manner as for compound () in Example 1.
I got it. This emulsion was added to 1 kg of a green-sensitive silver iodobromide emulsion (containing 6 moles of silver iodide), a hardening agent was added in the same manner as in the first layer of Example 1, and the emulsion was coated and dried. (Amount of coated silver: 20 mg/dm ² ) Fourth layer: Protective layer Gelatin layer containing 0.5 g/m ² of gelatin The sample thus obtained is referred to as (1), and the sample -
Samples 2 and 3 were prepared by adding coupler compound-2 and compound-6 of the present invention in an amount equivalent to 10% of the magenta coupler in the third layer of (1). Comparative samples-1 and 2 were prepared by adding the following comparative couplers instead of the couplers of the present invention.
and 3. Comparative coupler 1 Comparative coupler 1 of Example 1 Comparative coupler 2 Comparative coupler 2 of Example 1 Comparative coupler 3 Compound described in Research Disclosure No. 19536 After the sample thus obtained was wedge exposed to green light, the red density was increased by only exposure to red light.
Table 3 shows the results obtained by performing the same phenomenon treatment process as in Example 1 after uniform exposure with red light at an exposure dose of 2.0. The IIE (interlayer effect) on the red-sensitive layer was determined as follows. The red-sensitive layer is originally illuminated uniformly so that D=2.0, but IIE suppresses the development of the red-sensitive layer depending on the density developed in the green-sensitive layer, and the degree to which the red density decreases is determined by IIE. It is expressed. If the red density when the green density is maximum is D ₁ , then IIE
The strength of can be expressed as 2.0−D ₁ /2.0×100. That is, the larger this value, the stronger the IIE and the better the color reproducibility.

[Table] As can be seen from Table 3, the compounds of the present invention are
The improvement effect of IIE compared to similar comparative samples, i.e.
Great effect on improving color reproduction phenomenon. Even if the above embodiments are applied to a so-called false color negative film in which the sensitive wavelength range of the emulsion layer and the absorption wavelength range of the dye formed from the coupler contained in the emulsion layer are not in a complementary color relationship, almost the same results will be obtained. Got the results.

Claims (1)

[Claims] 1. A silver halide color photographic photosensitive material containing a non-diffusive coupling component capable of coupling with an oxidized form of a color developing agent and a photographic coupler having a diffusive substituent bonded at a position capable of being substituted by the coupling. In the material, when the diffusible substituent is released from the coupling component, it binds to the coupling component in a form that can couple with the oxidized color developing agent as a 4-equivalent coupler to form a dye. A silver halide color photographic material characterized by: