JPS6310818B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic material suitable particularly as a printing material. Prior art and its problems To form a color photographic image using a silver halide color photographic light-sensitive material (hereinafter simply referred to as "sensitive material"),
Normally, when an aromatic primary amine color developing agent reduces silver halide grains in the exposed light-sensitive material, it is itself oxidized, and this oxidized product is used as a coupler that is pre-contained in the light-sensitive material. This is done by reacting with the dye to form a dye image. Since couplers usually reproduce colors using the subtractive color method,
Three types of couplers are used to form three dyes: yellow, magenta, and cyan. Phenols are widely used as couplers for forming cyan dyes contained in photosensitive materials for printing. As one of the phenolic cyan couplers,
2,5-diacylaminophenol (e.g., U.S. Pat. No. 2,772,162, U.S. Pat. No. 2,895,826;
2369929 etc.). This 2,5-diacylaminophenol cyan coupler can be used even if the bleach bath or bleach-fix bath, which is mainly composed of ferric EDTA salt, is fatigued by running, resulting in loss of dye obtained by reaction with the color developing agent. It has extremely excellent characteristics in this respect. Moreover, the dye obtained from it has excellent heat resistance. However, the color forming properties of couplers are still unsatisfactory, and the dyes obtained have poor light resistance. 2,5-diacylaminophenol cyan couplers that overcome these drawbacks are described in US Pat. No. 3,758,308, US Pat. No. 3,880,661, and the like. Although such 2,5-diacylaminophenol 2-equivalent cyan coupler does improve color development to some extent and also improves the light fastness of the resulting dye, the unreacted remaining coupler causes light yellowing. It has disadvantages in that it causes problems in terms of color reproduction in the green area due to poor sharpness on the short wavelength side of the coloring dye. That is, the conventional 2,5-diacylaminophenol 2-equivalent cyan coupler (i) has a maximum absorption wavelength in the range of 640 to 660 nm, but has a large absorption in the green region of its absorption spectrum (particularly in the range of 500 to 550 nm), and (ii) )
The cyan dye formed does not have sufficient fastness to heat, light and moisture. Furthermore, (iii) the properties required for a cyan coupler, such as poor color development, could not be satisfied. Purpose of the Invention The present invention has been made in view of the above-mentioned circumstances, and has the following features: (i) absorption in the green region of the absorption spectrum is small, and the maximum absorption wavelength is at a long wavelength of 640 to 660 nm, and (ii) The cyan dye formed is heated,
It has sufficient fastness against light and moisture, and (iii)
To provide a silver halide color photographic light-sensitive material containing a cyan coupler which has good color development and does not lose dye even when a bleach bath or a bleach-fix bath is fatigued by running. Such an object is achieved by the present invention as described below. That is, it is realized by a silver halide color photographic light-sensitive material characterized by containing a compound represented by the following general formula as a cyan dye-forming coupler. general formula {In the general formula, R ₁ represents a linear or branched alkylene group having 1 to 8 carbon atoms, and Ar represents an aryl group having at least one alkyl group. } Further, a cyan dye-forming coupler represented by the following general formula [] is more preferably used. General formula [] {In the general formula [], R ¹ represents a linear or branched alkylene group having 1 to 8 carbon atoms,
R ² represents an alkyl group, and n is an integer of 1 to 3. When n is 2 or 3, R ² is
They may be the same or different. } Specific structure of the invention In the cyan coupler of the present invention represented by the above general formula [], the number of carbon atoms in R ¹ is 1 to 8, and even if R ¹ is a straight chain, it has a branch. However, in particular, the number of carbon atoms in R ¹ is 1 to
7 is preferred. Particularly preferred is one in which R ¹ is represented by -CH ₂ - |R, and R has 3 to 6 carbon atoms. On the other hand, as the alkyl group represented by R ² ,
The number of carbon atoms may be 1 to 20, such as methyl group, ethyl group, i-propyl group, butyl group,
t-butyl group, pentyl group, sec-pentyl group,
It may be any of t-pentyl group, t-octyl group, nonyl group, dodecyl group, sec-dodecyl group, octadecyl group, etc. One to three ^R2 's are bonded to the benzene ring, and when two or three R2's are bonded, each may be the same or different. However, it is preferable that the total number of carbon atoms of R ² or a plurality of R ² is 8 to 18. When R ¹ and R ² are groups other than those mentioned above, and furthermore, when the split-off group is other than Cl, the desired effects of the present invention will not be achieved. Next, typical examples of cyan couplers used in the present invention will be given, but the couplers used in the present invention are not limited thereto. Such a compound represented by the above general formula [] can generally be synthesized according to the following reaction formula. Here, R ⁰ is the above

[Formula]. Next, examples of synthesis of specific compounds will be shown. Synthesis Example 1 Coupler No. 2: 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5
-{5-α-(2,4-di-tert-amylphenoxy)-n-butanamide}phenol (A) 18.9 g (0.10 mole) of 2-amino-4-chloro-5-nitrophenol in 100 ml of acetonitrile Disperse 23.1g (0.10mole) of 2,
A solution of 3,4,5,6-pentafluorobenzoic acid chloride in 50 ml of acetone was added dropwise. After heating under reflux for 3 hours, the reaction solution was cooled on ice, the precipitated solid was collected, and after washing with cooled acetonitrile,
After drying, 32.5 g (yield: 85%) of 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5-nitrophenol was obtained. (B) 16 g (0.042 mole) of the above crude crystals were dissolved in 500 ml of alcohol, a palladium-carbon catalyst was added, and catalytic reduction with hydrogen was performed at room temperature and pressure. Next, the palladium-carbon catalyst was separated, and the oral liquid was concentrated. The residue was dissolved in 200 ml of acetonitrile and recrystallized to give 11 g of 2-(2,3,4,
5,6-pentafluorobenzamide)-4-
Chloro-5-aminophenol was obtained. (yield
74%) (C) 3.2 g (0.009 mole) of the above phenol derivative was added to a solution of 30 ml of acetic acid and 0.9 g of sodium acetate, and while stirring at room temperature, α-(2,4-di-tert-butylphenoxy)-n- Butanoic acid chloride 3.7
A solution of g of acetic acid (10 ml) was added dropwise. 30 at room temperature
After reacting for a minute, the mixture was poured into 300 ml of water and the precipitated solid was collected by filtration. Recrystallized from acetonitrile,
3.5 g (60% yield) of target coupler No. 2 was obtained.
The structure of the target product was confirmed by mass spectra, elemental analysis, and NMR spectra. Synthesis Example 2 Coupler No. 4: 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5
-{α-(2,4-di-tert-amylphenoxy)-n-hexamide}phenol Intermediate 2-(2,3,4,5,
6-Pentafluorobenzamide)-4-chloro-5-aminophenol (4.5 g) was added to a solution of 80 ml of acetic acid and 25 g of sodium acetate, and while stirring at room temperature, α-
A solution of 5.7 g of (2,4-di-tert-amylphenoxy)-n-hexanoyl chloride in 20 ml of acetic acid was added dropwise. After reacting for 30 minutes at room temperature, the mixture was poured into 300 ml of water and the precipitated solid was collected by filtration. Recrystallize with acetonitrile to obtain target coupler No. 4 with a melting point of 200-201℃.
I got it. Such couplers are generally lipophilic, and in order to incorporate them into a sensitive material, at least one compound represented by the general formula [ ] is dissolved in a high boiling point organic solvent as a so-called oil protector to remove the halogen of the sensitive material. It is contained in a silver oxide emulsion layer (generally a red-sensitive emulsion layer or a layer adjacent thereto). In order to incorporate the coupler of the present invention into the emulsion layer of a color sensitive material, a conventionally known method can be used.
After dissolving the coupler of the present invention in a low boiling point solvent such as butyl propionate alone or in a mixture thereof as necessary,
The silver halide emulsion used in the present invention can be prepared by mixing it with an aqueous gelatin solution containing a surfactant, then emulsifying it in a high-speed rotary mixer or a colloid mill, and then adding it to silver halide. In this way, when the above-mentioned coupler is contained in the photosensitive layer of a photosensitive material, it has the advantage of improving color staining etc. because it shows no bad interaction with color development and has particularly good reactivity. . Furthermore, the dye obtained using the coupler of the present invention satisfies the above-mentioned excellent color absorption properties. The photosensitive layer (silver halide emulsion layer) of the photosensitive material containing the cyan coupler according to the present invention is generally red-sensitive, and the silver halides used include silver bromide, silver chloride, and silver iodobromide. , silver chlorobromide, silver chloroiodobromide, and any other materials used in ordinary silver halide emulsions are included. The silver halide emulsion constituting the silver halide emulsion can be manufactured by the usual manufacturing method,
Various manufacturing methods, such as those described in Japanese Patent Publication No. 46-7772, or U.S. Pat.
No. 2,592,250, ie, forming an emulsion of silver salt grains consisting of at least a portion of a silver salt whose solubility is greater than that of silver bromide, and then at least a portion of the grains being treated with a silver bromide salt or It can be produced by any production method, such as a so-called compound emulsion production method, such as conversion to silver iodobromide salt, or a Lipman emulsion production method, which consists of fine-grained silver halide having an average grain size of 0.1 μm or less. In addition, the silver halide emulsions may contain sulfur sensitizers, such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers, such as stannous salts, polyamines, etc., noble metals. Sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc., or, for example, ruthenium,
Chemical sensitization can be carried out using water-soluble salt sensitizers such as rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadide, alone or in combination as appropriate. Further, the silver halide emulsion can contain various known photographic additives. The silver halide containing the coupler of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart sensitivity to the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
No. 2269234, No. 2270378, No. 2442710, No.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of No. 2454629 and No. 2776280. Such red-sensitive emulsion layers are generally provided on a reflective support. Then, it is usually laminated with other known green-sensitive and blue-sensitive emulsion layers according to a known method to form a light-sensitive material. Specific Uses of the Invention The photosensitive material of the present invention is usually exposed to light through a photographic photosensitive material and then developed with a color developing solution.
A preferred color developing agent is one containing an aromatic primary amine color developing agent as a main component. A typical example of this color developing agent is p-phenylenediamine, such as diethyl-p
-phenylenediamine hydrochloride, monomethyl-p-
Phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N
-ethyl-N-dodecylamino)-toluene, 2
-amino-5-(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 4
-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N
-β-hydroxyethylamino)aniline, 2-
Examples include amino-5-(N-ethyl-N-β-methoxyethyl)aminotoluene. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, color developers generally contain alkaline agents such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate, sodium sulfite, etc., and various additives such as alkali metal halides such as potassium bromide, or development regulators such as It may also contain cidradinic acid and the like. Next, various known processing is performed to obtain a color photographic image. Specific Effects of the Invention According to the present invention, a cyan color line image having a maximum absorption wavelength of 640 to 660 nm can be obtained, and moreover,
Absorption at ~550 nm is very small, giving very good cyan dye images. The dyes formed are also extremely robust to heat, light, and moisture. Furthermore, the coloring property is also very good. In addition, even if the bleach or bleach-fix bath is fatigued by running, there is very little loss of dye. The present inventors conducted various experiments to confirm the effects of the present invention. An example is shown below. Experimental Example 1 Using couplers of the present invention and comparative couplers as shown in Table 1 below, 10 g of each coupler was added to a mixture of 5 ml of dibutyl phthalate and 30 ml of ethyl acetate, and heated to 60°C to completely dissolve the couplers. dissolved in This solution was mixed with 5 ml of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 ml of a 5% aqueous solution of gelatin.
A dispersion of each coupler was prepared by emulsification using a colloid mill. This coupler dispersion was then added to 500 g of gelatin-silver chlorobromide (containing 20 mol% silver bromide) emulsion, coated on polyethylene coated paper, and dried to form six types of silver halide color photographic light-sensitive materials. It was created. These samples were subjected to wedge exposure according to a conventional method and then subjected to the following processing. Color development process Color development 30°C 3 minutes 30 seconds Bleach fixing 30°C 1 minute 30 seconds Washing 30°C 2 minutes The composition of each processing solution in the color development process is as follows. Color developer composition 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5g Benzyl alcohol 15ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Sodium bromide 1.4g Potassium bromide 0.5g Borax 39.1g Add water to make 1 and hydroxide Adjust the pH to 10.3 using sodium. Bleach-fix composition Ethylenediaminetetraacetic acid iron ammonium salt
61.0g Ethylenediaminetetraacetic acid diammonium salt
5.0 g Ammonium thiosulfate 124.5 g Sodium metabisulfite 13.5 g Anhydrous sodium sulfite 2.7 g Add water to make up to 1 Photographic properties were measured for each sample obtained after processing. The results are shown in Table 1. Note that the sensitivity values in the table are expressed as relative sensitivities with the sensitivity of sample No. 1 as 100. For this measurement, a PDA-60 type densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) was used. In addition, "D (λ550)" in the table evaluates the short wavelength side of the reflection spectrum after coloring of the cyan coupler, and the wavelength when the density of the maximum reflection spectrum after cyan coloring is 1.6. This shows the reflection density at 550nm. This indicates the influence of the cyan coupler on the color reproducibility of the green area after color development, and since human visibility is particularly high in this area, this "D(λ550)"
To the human eye, even a slight change in the value of is perceived as a large change in tone, and from the viewpoint of photographic performance and color reproducibility of green areas, it is preferable that this value is as small as possible.

[Table] As is clear from Table 1, the cyan coupler according to the present invention has spectral reflection characteristics (maximum reflection wavelength and D (λ550)) favorable for photographic performance, and the human visibility in the green-sensing area is low. The photographic performance was significantly improved and exhibited photographic performance unmatched by the prior art. Furthermore, when compared with any of the comparative couplers, it shows a higher color density, indicating that it is a cyan coupler with extremely good photographic properties. Experimental Example 2 Samples 7 to 12, in which six types of cyan dye images were formed, were obtained in the same manner as in Experimental Example 1 using the couplers of the present invention and comparative couplers as shown in Table 2. Then, we examined light resistance, heat resistance, and moisture resistance. The results obtained are shown in Table 2. In addition, light resistance is determined after 200 hours of exposure of each image using a xenon fade meter, heat resistance is determined after 2 weeks at 77℃, and humidity resistance is determined after 2 weeks at 60℃ and 70% relative humidity. The respective residual concentrations at the initial concentration of 1.0 are shown. (Each residual density %) In addition, stain is expressed as a percentage increase in blue density in the unexposed area of the sample subjected to the light resistance test.

[Table] As is clear from Table 2, the comparative coupler (D) is
Heat resistance and moisture resistance are extremely poor, and comparative coupler (C) has extremely poor light resistance. In addition, the comparative coupler (B), which showed relatively good results among the comparative couplers in Experimental Example 1,
It can also be seen that the stain deteriorated significantly and the light resistance, heat resistance, and moisture resistance were inferior to the cyan coupler according to the present invention. It can be seen that the cyan coupler according to the present invention has extremely excellent performance in these respects as well.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material containing a compound represented by the following general formula as a cyan dye-forming coupler. general formula {In the general formula, R ₁ represents a linear or branched alkylene group having 1 to 8 carbon atoms, and Ar is
Represents an aryl group having at least one alkyl group. }