JPH0515249B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic material containing a novel phenolic cyan coupler. [Background of the Invention] Generally, silver halide color photographic light-sensitive materials consist of three types of photographic silver halide that are selectively spectral sensitized to have sensitivity to blue light, green light, and red light on a support. An emulsion layer is coated. For example, in silver halide photographic materials for color negatives, generally a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the exposed side. A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer in order to absorb the blue light that passes through the blue-sensitive silver halide emulsion layer. It is provided. moreover,
Each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various special purposes. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. Similar to silver halide photographic materials for color negatives, intermediate layers such as an ultraviolet absorbing layer and protective layers are provided for special purposes. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and each silver halide emulsion layer is further provided with
It is also known to use a light-sensitive silver halide emulsion layer consisting of two layers sensitive to substantially the same wavelength range for each color light. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, in order to form cyan, magenta and yellow dye images, phenolic or naphthol cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles,
Indazolone or cyanoacetyl magenta couplers and acylacetamide yellow couplers are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developer. Many phenolic cyan couplers that form cyan dyes have been known in the past. For example, 2-(α-
The coloring dye formed from 2,4-di-tert-amylphenoxybutanamide)-4,6-dichloro-5-methylphenol has good light resistance, but has poor heat resistance and recolorability. It has the disadvantage of being inferior. Furthermore, 6-(2,
4-di-tert-amyl-6-chloro-phenoxyacetamide)-2,4-dichloro-3-ethylphenol and Exemplary Compound 30 described in JP-A-58-95346 also showed that the heat resistance of images was improved to some extent. However, it is still insufficient. Furthermore, conventional couplers are used by dissolving them in high boiling point solvents, but US Pat.
Since the above coupler described in No. 95346 has poor solubility and problems with its dispersion state, it is difficult to obtain the desired color density. Regarding the so-called 2,5-dialmylaminophenol type cyan couplers described in JP-A-53-109630 and JP-A-50-134644, the dye has good heat resistance but insufficient light resistance. , and the spectral absorption characteristics are insufficient. [Object of the Invention] The first object of the present invention is to provide a silver halide photographic material containing a cyan coupler with excellent color development. A second object of the present invention is to provide a silver halide photographic material capable of forming cyan images with excellent light fastness, heat resistance and color reversibility. [Structure of the Invention] The above object of the present invention can be achieved by incorporating a cyan coupler represented by the following general formula [] into a silver halide photographic light-sensitive material. General formula [] [In the formula, R ₁ is an alkyl group having 2 or 4 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.
In the alkyl group of 4 to 4, X represents a halogen atom, an alkoxy group or an aryloxy group. ] [Specific structure of the invention] The cyan coupler represented by the general formula [] will be explained. In the general formula [], the number of carbon atoms in the alkyl group represented by R ₁ , R ₂ and R ₃ is the number of carbon atoms excluding the substituent when these alkyl groups have a substituent. . In the general formula [ ], examples of the alkyl group having 2 to 4 carbon atoms represented by R ₁ include ethyl group, propyl group, iso-propyl group, butyl group, t-butyl group, etc. is preferred. Examples of the alkyl group having 1 to 16 carbon atoms represented by _R2 include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, Examples include a hexadecyl group, but an alkyl group having 2 to 12 carbon atoms is preferred. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ₃ include methyl group, ethyl group, propyl group, butyl group, and iso-propyl group. Preferred R ₃ is a hydrogen atom. Also, R ₁ ,
The alkyl groups represented by R ₂ and R ₃ each include those having a substituent. X represents a halogen atom, an alkoxy group, or an aryloxy group that can be separated during a coupling reaction with an oxidized color developing agent; examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, etc. Among these, chlorine atoms are particularly preferred. Alkoxy groups include those with substituents, such as methoxy groups, ethoxy groups, β-
Examples include methanesulfonylethoxy group, β-methoxyethylcarbamoylmethoxy group, and the like. Aryloxy groups include those having substituents, such as phenoxy group, p-methoxyphenoxy group, and the like. Typical specific compounds of the present invention are illustrated below, but the compounds of the present invention are not limited thereto. Synthesis of exemplary compounds of the present invention is shown below, but other exemplary compounds can also be synthesized by similar methods. Synthesis of Exemplified Compound C-1 (1)-a Synthesis of 2-nitro-4,6-dichloro-5-ethylphenol 33 g of 2-nitro-5-ethylphenol, 0.6 g of iodine and 1.5 g of ferric chloride were Dissolve in 150ml of acetic acid. Add sulfuryl chloride to this at 40℃.
Drop 75ml over 3 hours. The precipitate formed during the dropwise addition is reacted and dissolved by heating and refluxing after the completion of the dropping of sulfuryl chloride.Heating and refluxing takes about 2 hours. The reaction solution is poured into water and the crystals formed are purified by recrystallization with methanol. (1)
-a was confirmed by nuclear magnetic resonance spectroscopy and elemental analysis. (1)-b Synthesis of 2-amino-4,6-dichloro-5-ethylphenol (1)-a 21.2g was dissolved in 300ml of alcohol,
A catalytic amount of Raney nickel was added to this, and hydrogen was passed through it at normal pressure until no more hydrogen was absorbed. After the reaction, Raney nickel was removed and the alcohol was distilled off under reduced pressure. The residue (1)-b was subjected to the next acylation without being purified. (1)-c Synthesis of Exemplified Compound C-1 18.5 g of the crude amino compound obtained in (1)-b was
It is dissolved in a mixture of 500 ml of glacial acetic acid and 16.7 g of sodium acetate, and an acetic acid solution prepared by dissolving 34.2 g of m-pentadecylphenoxyacetic acid chloride in 70 ml of acetic acid is added dropwise thereto at room temperature. Drip in 30 minutes,
After stirring for an additional 30 minutes, the reaction solution was poured into ice water.
The generated precipitate is collected by filtration, dried, and then recrystallized twice from a hexane/ethyl acetate mixed solvent to obtain the desired product. The target product was confirmed by elemental analysis and nuclear magnetic resonance spectroscopy. C ₃₁ H ₄₅ NO ₃ Cl ₂ C H N Cl (%) Calculated value 67.62 8.24 2.53 12.28 Measured value 67.36 8.27 2.41 12.99 The methods and techniques used for ordinary cyan couplers can be applied to the cyan coupler used in the present invention. I can do it. Typically, a cyan coupler is contained in a silver halide emulsion, and this silver halide emulsion is coated on a support to form a silver halide photographic light-sensitive material. Silver halide photographic materials can be used for monochrome or multicolor use. Silver halide color photographic materials usually have silver halide emulsion layers sensitive to each of the three primary color regions of the spectrum. The silver halide emulsion layer can consist not only of a single emulsion layer but also of multiple emulsion layers. The photographic constituent layers can be arranged in various orders as is known in the art. A typical silver halide color photographic light-sensitive material has a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler. is supported on a support. In addition to these photosensitive silver halide emulsion layers, for example, a filter layer, an intermediate layer,
It can have a protective layer, an undercoat layer, etc. Various methods can be used to incorporate the cyan coupler of the present invention into a silver halide emulsion layer. For example, the cyanide of the present invention may be added to a high boiling point organic solvent with a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate, or a low boiling point solvent such as butyl acetate or butyl propionate, or a mixture thereof as necessary. After the couplers are dissolved alone or in combination, they are mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotary mixer or colloid mill, and then added to the silver halide to form the halogen used in the present invention. A silver oxide emulsion can be prepared.
When the cyan coupler of the present invention is added to a silver halide emulsion, usually silver halide 1
about 0.07 mole to 0.7 mole per mole, preferably
0.1 mole to 0.4 mole is added. Silver halide used in the silver halide photographic material of the present invention includes silver bromide, silver chloride,
Any of those used in conventional silver halide emulsions, such as silver iodobromide, silver chlorobromide, and silver chloroiodobromide, are included. The silver halide emulsion used in the present invention can be produced by a variety of methods including the usual method, such as the method described in Japanese Patent Publication No. 46-7772, in which the solubility is higher than that of silver bromide.
A method of manufacturing a so-called conversion emulsion, such as forming an emulsion of silver salt grains consisting of at least a portion of silver salt, and then converting at least a portion of the grains to silver bromide or silver iodobromide salt, or a method of manufacturing a so-called conversion emulsion, or a method of manufacturing a silver salt grain of 0.1μ or less. It can be produced by any production method such as the Lipman emulsion production method consisting of fine-grained silver halide having an average grain size of . Furthermore, the silver halide emulsion used in the present invention 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 metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc., or water-soluble materials such as rutinium, rhodium, iridium, etc. Chemical sensitization can be carried out using a sex salt sensitizer, specifically ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadide, etc. alone or in combination as appropriate. Further, the silver halide emulsion used in the present invention can contain various known photographic additives. For example, Research Disclosure December 1978 Item 17643
Photographic additives such as those described in . The silver halide emulsion used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye, for example, in order to impart photosensitivity in the sensitive wavelength range necessary for a red-sensitive emulsion. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral sensitizing dyes that are advantageously used in the present invention include, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of the same No. 2776280. The color developing solution that can be used in the present invention preferably has an aromatic primary amine color developing agent as a main component. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Diamine 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-amino-5-(N-ethyl-N-β-methoxyethyl)aminotoluene, and the like. Development is followed by the usual steps of bleaching, fixing or bleach-fixing, washing and drying to remove silver and silver halides. [Examples] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 A silver halide color photographic material was prepared by sequentially coating the following layers on polyethylene resin coated paper. (Hereinafter, in all Examples, the amounts added to silver halide color photographic light-sensitive materials are shown ^per 100 cm2.) (1) 16 mg gelatin, 4 mg red-sensitive silver chlorobromide emulsion, 7 x 10 ^-6 moles of exemplary cyan coupler C-2
(2) a gelatin protective layer containing 9 mg gelatin; The sample of the present invention prepared as described above was designated as Sample-1. On the other hand, sample 2 was prepared in the same manner as sample 1 except that comparative couplers A, B, C, and D shown below were used in place of the exemplified cyan coupler C-2 of the present invention. , 3, 4 and 5. Samples-1, 2, 3, 4 and 5 were exposed to a light wedge according to the sensitometric method and then processed at a temperature of 33 DEG C. according to the following sequence. Processing steps Color development: 3 minutes and 30 seconds Bleach-fixing: 1 minute and 30 seconds Washing with water: 3 minutes As the color developer and bleach-fix solution, processing solutions having the following formulations were used. Color developer formulation N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
4.9g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Benzyl alcohol 13ml Polyethylene glycol (average degree of polymerization 400) 3.0ml Add water to 1 and add sodium hydroxide to pH 10.0
Adjust to. Bleach-fix solution formulation ethylenediaminetetraacetic acid iron sodium salt
6.0g Ammonium thiosulfate 100g Sodium bisulfite 10g Sodium metabisulfite 3g Add water to make 1, and adjust the pH to 7.0 with aqueous ammonia. The density of the obtained cyan image was measured using a densitometer (Model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.), and the sensitivity, fog, and maximum density (Dmax) were determined. In addition, samples 1 to 5 subjected to the above treatment were irradiated with a xenon fade meter for 8 days to examine the light resistance of the color image, and were stored in a high temperature atmosphere of 77°C for 2 weeks to examine the heat resistance of the color image. Ta. The numerical values in the table indicate the percentage of dye remaining after processing at the initial density D=1.0. The results obtained are shown in Table 1.
(However, the sensitivity is the relative sensitivity when the sensitivity of sample 1 is set as 100.)

[Table] From Table 1, it can be seen that comparative coupler A has extremely poor heat resistance, and although comparative couplers B and C have considerably improved heat resistance than comparative coupler A, it is still insufficient. Furthermore, it was observed that Comparative Couplers B and C had poor dispersion because they were poorly dissolved during coupler dispersion. As a result, as shown in Table 1, the color development was also slightly lower than that of other couplers. Comparative coupler D showed significant deterioration in optical properties. On the other hand, the sample using the exemplary coupler C-2 according to the present invention showed good results in all of color development, color image translucency, and heat resistance. Example 2 Exemplary coupler of the invention -C- as a coupler used
Samples 6, 7, 8, 9 and 10 were created. These samples were subjected to exactly the same method as in Example 1, and the results shown in Table 2 were obtained.

[Table] From Table 2, exemplary couplers-C- according to the present invention
It can be seen that the samples prepared using C-4, C-6, C-13, and C-19 are excellent in color development, light resistance of color images, and heat resistance. Example 3 The degree of cyan dye loss (color restorability) of all the couplers studied in Examples 1 and 2 during fatigue bleach-fixing treatment was investigated. A model fatigue bleach-fix solution was used as the fatigue bleach-fix solution, which was prepared by adding silver powder to the bleach-fix solution used in Example 1 to lower the potential and further lower the pH. Bleach-fix solution Fatigue bleach-fix solution Potential -20mV Potential -100mV PH7.0 PH6.3 (A silver-silver chloride electrode was used to measure the potential.) Recolorability is the Dmax obtained by fatigue bleach-fixing.
is expressed as the value obtained by dividing Dmax obtained in the treatments of Examples 1 and 2. (Displayed in %) The results obtained are shown in Table 3.

【table】

[Table] From Table 3, it can be seen that comparative coupler A has extremely poor color recovery properties in fatigue bleach-fixing treatment, and comparative couplers B and C are also considerably improved over A, but are still insufficient. . Comparative coupler D is a coupler with extremely good recoloring properties, but as can be seen from Example 1, it has the drawback that the light resistance of the dye is extremely poor. On the other hand, in the case of samples-1, 6, 7, 8, 9 and 10 prepared using the cyan coupler according to the present invention, the recoloring property is slightly lower than that of sample-5 prepared using comparative coupler D. , showing quite good values. Moreover, in the case of these samples of the present invention, as is clear from Examples 1 and 2, color development,
Both the light resistance and heat resistance of the dye are extremely excellent. Example 4 A silver halide color photographic material was prepared by sequentially coating the following layers on polyethylene resin-coated paper containing anatase-type titanium oxide. The amounts added below are per ^100cm2 . (1) 20 mg of gelatin, 5 mg of silver as a blue-sensitive chlorobromide emulsion, and 8 mg of Y-coupler and
Layer containing 3 mg di-octyl phthalate coupler solvent in which 0.1 mg 2,5-di-t-octylhydroquinone is dissolved (2) 12 mg gelatin, 0.5 mg 2,5-di-t-octylhydroquinone and 4 mg UV absorbing An intermediate layer containing 2 mg of dibutyl phthalate UV absorber solvent dissolved therein. (3) 18 mg of gelatin, 4 mg of green-sensitive silver chlorobromide emulsion, and 5 mg of M-coupler and 2 mg of silver.
of antioxidant and 0.2 mg of 2,5-di-t-
A layer containing 2.5 mg of dioctyl phthalate coupler solvent in which octyl hydroquinone was dissolved. (4) An intermediate layer containing the same composition as (2). (5) 16 mg of gelatin, 4 mg of silver as a red-sensitive silver chlorobromide emulsion, and 2.0 mg of tricresyl in which 3.5 mg of C-coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved. Layer containing phosphate coupler solvent. (6) Gelatin protective layer containing 9 mg of gelatin. Coating aids are added to each layer (1) to (6), and (4)
A gelatin crosslinking agent was added to layer (6). As the ultraviolet absorber (2) and (4), 2-(2'-hydroxy-3',5'-di-t-aminophenyl)
-benzotriazole and 2-(2'-hydroxy-
An equimolar mixture of 3',5'-di-t-butylphenyl)benzotriazole was used. As the antioxidant (3), di-t-pentylhydroquinone di-octyl ether was used. The above multilayer photosensitive material was processed in the same manner as in Example 1. Table 4 shows the Y-coupler, M-coupler, and C-coupler used in each layer and the results. Each sample was measured for cyan density after exposure to white light. In addition, the same treatment as in Example 3 was performed for color restoration.

【table】

From the results in Table 4, even in silver halide photographic materials with a multilayer structure, samples using the cyan coupler according to the present invention have good color development, light fastness of dye images, heat resistance, and color recovery. I understand that there is something. Example 5 Same as Sample No. 1 of Example 4 except that each coupler in layer (1), layer (3), and layer (5) of Sample No. 1 of Example 4 was replaced with the coupler listed in Table-5. A sample was prepared. (However, in samples 5 to 8, layer (0) was provided between layer (1) and the support. Each sample was exposed to white light and then treated in the same manner as in Example 1. However,
The color development times were 1 minute, 1 minute 30 seconds, and 3 minutes 30 seconds. The maximum concentrations of Y, M, and C at that time were measured. The results are shown in Table 5. [Layer [0]: 3 mg of an ethanol solution of the following compound P-1 was dispersed in 20 mg of gelatin. ]

[Table] From the results in Table 5, it can be seen that the sample using comparative coupler (A) was treated with cyan coupler C of the present invention for 3 minutes and 30 seconds.
-2 shows almost the same color development as the sample using
Rapid processing significantly deteriorates the color development, and using additive P-1 (Samples 5 and 7) improves the color development, but the color development is still poor compared to the case of 3 minutes and 30 seconds of processing. will result in inferior results. On the other hand, the sample using the cyan coupler C-2 of the present invention has good dispersibility of the cyan coupler, so
Even when high color development is obtained and rapid processing is performed, when additive P-1 is used, color development almost close to that obtained in the case of 3 minutes and 30 seconds processing can be obtained. Example 6 Except that the support of each of Samples 1 to 5 in Example 4 was replaced with a support obtained by polymerizing an olefin compound containing 20% by weight or more of titanium oxide on a paper support with an electron beam. A multilayer coating sample similar to that in Example 4 was prepared and subjected to the same treatment as in Example 1. The results of processing each sample were all satisfactory, with both excellent sharpness and smoothness. Excellent results were also obtained when a polyethylene terephthalate support into which titanium oxide was incorporated was used as the support.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing a cyan coupler represented by the following general formula []. General formula [] [In the formula, R ₁ is an alkyl group having 2 or 4 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.
In the alkyl group of 4 to 4, X represents a halogen atom, an alkoxy group or an aryloxy group. ]