JPH0458014B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material containing a phenolic cyan coupler. Prior Art and its Problems Generally, in silver halide color photographic light-sensitive materials, a color image is obtained by a coupling reaction between an oxidation product of a color developing agent and a coupler to form a color dye. Among these, multicolor silver halide photographic light-sensitive materials usually use a subtractive color method to form color images, and the dye produced by the coupling reaction is a silver halide that is sensitive to the wavelength range of light absorbed by the image dye. Cyan, magenta and yellow dyes are typically formed in or adjacent to emulsion layers, ie, silver halide emulsion layers sensitive to each of the red, green and blue regions of the spectrum. Couplers typically used to form cyan dyes are phenols and naphthols. In particular, the basic properties required for phenols are that the spectral absorption characteristics of the cyan dye are good, that is, there is no absorption in the green region of the spectrum, and the half-value width (maximum density and dye fog) of the absorption spectrum curve in the red region. (wavelength width at the middle absorbance area) is narrow and sharp. The cyan dye formed has sufficient fastness against light, heat, moisture, etc. It should have good color development, that is, it should have sufficient color development sensitivity and color density. Furthermore
One example is that a bleach bath or bleach-fix bath containing EDTA ferric salt as a main component does not cause loss of color even when fatigued by running. Furthermore, from the viewpoint of depollution, the removal of benzyl alcohol added to color developing solutions has been taken up as a major problem. However, the current situation is that sufficient color development cannot be obtained with Ancapular unless benzyl alcohol is added. The decrease in color development when benzyl alcohol is not added is particularly noticeable in phenolic cyan couplers, and from this point of view as well, there is a demand for phenolic cyan couplers that exhibit high color development even without benzyl alcohol. Research has been conducted on various phenolic cyan couplers to satisfy the above requirements, but to the best of the inventors' knowledge, no cyan coupler has yet been found that can satisfy all of the above requirements. The current situation is that there is no such thing. For example, 6-[α(2,4-di-t-amylphenoxy) described in U.S. Pat. No. 2,801,171
[Ptanamide]-2,4-dichloro-3-methylphenol has good light resistance, but has a drawback in heat resistance and also suffers from large dye loss in a tired bleach-fix solution. Furthermore, color development is highly dependent on benzyl alcohol, and it is difficult to remove benzyl alcohol from a color developer. 2-heptafluorobutanamide-5-[α-(2,4-
Di-t-amylphenoxy)hexaneamide]phenol is superior in terms of heat resistance and dye loss in a fatigued bleach-fix bath, but inferior in terms of light resistance and color development. Furthermore, the phenolic cyan coupler described in JP-A-53-109630 also has problems in terms of removal of benzyl alcohol and light resistance. Furthermore, U.S. Patent No. 3839044, JP-A-47-37425, and JP-A-48-36894
No. 50-10135, No. 50-117422, No. 50
The phenolic cyan couplers described in Publications No. 130441, No. 50-108841, and No. 50-120334 are also insufficient in terms of heat resistance and removal of benzyl alcohol. Phenol cyan couplers having a ureido group at the 2-position are described in British Patent No. 1011940, U.S. Patent No. 3446622, U.S. Patent No. 3996253, U.S. Patent No. 3758308, and U.S. Patent No. 3880661, etc.
The cyan dye formed from these cyan couplers has a wide half-width of the absorption spectrum curve in the red region, and furthermore, the absorption maximum is in the relatively short wave region of the red region, so it has considerable absorption in the green region of the spectrum. Unfavorable for color reproduction. Although the phenolic cyan coupler having a ureido group at the 2-position described in JP-A-56-65134 has considerably improved absorption in the green region,
Other characteristics are still insufficient. OBJECTS OF THE INVENTION The first object of the present invention is that the absorption maximum wavelength of the cyan dye image to be formed is on the long wavelength side of the red absorption spectral region, and the half-width of the absorption spectral curve in the red region is narrow. An object of the present invention is to provide a silver halide photographic material from which cyan dye images with excellent color reproducibility can be obtained. A second object of the present invention is to provide a silver halide photographic material capable of producing cyan dye images that are robust against light, heat, moisture, and the like. A third object of the present invention is to provide a silver halide photographic material that exhibits extremely little loss of dye even when processed in a tired bleach bath or bleach-fix bath. The fourth object of the present invention is to have good color development,
It is an object of the present invention to provide a silver halide photographic material that exhibits good color development even when developed without using benzyl alcohol and provides images with excellent sensitometric properties. The above object of the present invention is to provide at least one
In a silver halide photographic light-sensitive material provided with a silver halide emulsion layer, a phenolic cyan coupler represented by the following general formula [] is contained in at least one of the silver halide emulsion layers. achieved. General formula [] [In the formula, Ar is a halogen atom, an alkyl group, an alkoxy group, an acyloxy group, a hydroxycarbonyl group, an alkylthio group, an alkylsulfonyl group, an acylamino group, a sulfamide group, and a carbamoyl group. Represents a phenyl group at the para position. X represents an oxygen atom or a sulfur atom. R
represents an alkylene group. Y represents a halogen atom. n represents an integer of 1 or 2. However, n
When is 2, Y may be the same or different. Z represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. ] However, if the cyan coupler and Except when only [X represents H, ^COOR3 , an alkoxy group, a halogen atom, ^R1 , ^R2 , ^R3 each represents an alkyl group having 1 to 20 carbon atoms] is used as a solvent for the cyan coupler. In addition, in this specification, when describing a group into which a substituent can be introduced, such as an alkyl group, an alkoxy group, a phenyl group, or an alkylene group, unless otherwise specified, those substituents will be referred to. The group into which can be introduced includes both those having a substituent and those having no substituent. DETAILED DESCRIPTION OF THE INVENTION In the present invention, the halogen atom mentioned as a substituent of the phenyl group having a substituent represented by Ar in the general formula [] is, for example, fluorine, chlorine, bromine, etc., and the alkyl group is directly Chain or branched, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t
-pentyl group, neo-pentyl group, n-octyl group, i-octyl group, sec-octyl group, t-octyl group, n-dodecyl group, i-dodecyl group,
sec-dodecyl group, t-dodecyl group, n-hexadecyl group, i-hexadecyl group, sec-hexadecyl group, t-hexadecyl group, n-octadecyl group, i-octadecyl group, sec-octadecyl group,
t-octadecyl group, etc. When these alkyl groups have a substituent, the substituent is
Typical examples include halogen atoms (e.g. fluorine,
chlorine, bromine, etc.), aryl groups (e.g. phenyl group,
tolyl group, naphthyl group, etc.), hydroxyl group, carboxyl group, alkoxycarbonyl group, alkylthio group, alkoxy group, etc. Ar
The alkoxy group mentioned as a substituent of the phenyl group having a substituent represented by is a straight chain or branched alkyloxy group, such as a methoxy group, an ethoxy group, an n-propyloxy group, an n-butyloxy group, a t- Examples of the acyloxy group include a butyloxy group, a benzyloxy group, and an arylcarbonyloxy group such as a linear or branched alkylcarbonyloxy group such as an acetyloxy group and an n-dodecycarbonyloxy group, and a benzoyloxy group. . The alkylthio group listed as a substituent for the phenyl group having a substituent represented by Ar is
A straight-chain or branched alkylthio group, such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, t
-butylthio group, n-octylthio group, n-dodecylthio group, n-hexadecylthio group, n-octadecylthio group, etc., and the alkylsulfonyl group is a linear or branched alkylsulfonyl group, such as methylsulfonyl group, ethyl Sulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, t-butylsulfonyl group, n-dodecylsulfonyl group,
These include n-pentadecylsulfonyl group, n-hexadecylsulfonyl group, benzylsulfonyl group, and the like. The acylamino group mentioned as a substituent of the phenyl group having a substituent represented by Ar is, for example, n-undecylcarbonylamino group, n-dodecylcarbonylamino group, n-hexadecylcarbonylamino group, n-octadecylcarbonylamino group. straight-chain or branched alkylcarbonylamino groups such as, arylcarbonylamino groups such as benzoylamino groups, etc. The sulfamide group mentioned as a substituent for the phenyl group having a substituent represented by Ar is, for example, a linear or branched alkylaminosulfonamide group such as an N,N-dimethylaminosulfonamide group, an anilinosulfonamide group, etc. An arylaminosulfonamide group, etc.
The carbamoyl group is, for example, i-dodecylcarbamoyl group, n-hexadecylcarbamoyl group, n-
These include straight-chain or branched alkylcarbamoyl groups such as an octadecylcarbamoyl group, and arylcarbamoyl groups such as a phenylcarbamoyl group. The substituent of the phenyl group having the substituent represented by Ar may be introduced into at least one of the ortho position or the rose position of the phenyl group. Furthermore, the above-mentioned substituents may be present in the ortho group, para-position, or meta-position of the phenyl group to which the above-mentioned substituents have not been introduced, and substituents other than the above-mentioned substituents, such as hydroxyl groups, aryl groups, heterocyclic group, cyano group, nitro group, etc. may be introduced. In the general formula [], X is preferably an oxygen atom. The alkylene group represented by R in the general formula [] is preferably a straight chain or branched alkylene group having no substituents, more preferably a straight chain or branched alkylene group having 1 to 20 carbon atoms. It is an alkylene group that does not. Even more preferably, R is

〔process〕

Processing steps (30°C) Processing time Color development: 3 minutes and 30 seconds Bleach-fixing: 1 minute and 30 seconds Washing with water: 2 minutes The composition of each treatment is shown below. [Color developer composition 1] 4-amino-3-methyl-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 5.0g Benzyl alcohol 15.0ml 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, then water Adjust the pH to 10.30 using sodium oxide. [Color developer composition 2] 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.0g 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 use sodium hydroxide. and adjust the pH to 10.30. [Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
50g ammonium sulfite (40% solution) 50ml ammonium thiosulfate (70% solution) 140ml aqueous ammonia (28% solution) 20ml ethylenediaminetetraacetic acid 4g Add water to make 1. Photographic properties were measured for each of the obtained samples. The results are shown in Table 1. In the table, the relative density values are expressed with the maximum sensitivity value when processed with color developer [1] as 100.

【table】

[Table] As is clear from the above Table 1, the samples obtained using the phenolic cyan coupler according to the present invention are excellent in that good sensitivity and maximum concentration can be obtained regardless of the presence or absence of benzyl alcohol. Further, as a result of measuring the color spectrum, it was found that the dye using the phenolic cyan coupler according to the present invention has a maximum absorption maximum in a relatively long part of the red region, and the absorption on the short wavelength side shows at least excellent color purity. It turned out that. Example (2) Using samples obtained in the same manner as in Example (1) above, the light resistance, heat resistance, and moisture resistance of dye images were investigated. The results obtained are shown in Table 2.

【table】

〔process〕

Processing process (33℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilization 1 minute 30 seconds [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/8 sulfate 1.98g Sulfuric acid 0.74ml Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitriloacetic acid 3 Sodium salt 1.20g Potassium hydroxide 1.48g Add water to make 1. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100g Ethylenediaminetetraacetic acid diammonium salt
10g ammonium bromide 150g glacial acetic acid 10ml Add water to make 1, then use ammonia water to pH
Adjust to 6.0. [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 photographic properties of the resulting cyan-colored image were measured, as well as the maximum absorption wavelength (λ _nax ) in the area where the density is 1.0 and the half-value width (the width of the wavelength in the area where the difference between the maximum density and the dye fog is 1/2). . The results are shown in Table 3.

[Bleach-fix solution composition]

Ethylenediaminetetraacetate iron ammonium salt
50g ammonium sulfite (40% solution) 50ml ammonium thiosulfate (70% solution) 140ml aqueous ammonia (28% solution) 20ml ethylenediaminetetraacetic acid 4g hydrosulfite 5g Add water to make 1. The maximum reflection density of the cyan dye of the sample obtained after the development process was measured. The results are shown in Table 4. Incidentally, the dye residual rate at the maximum density portion was determined as follows. Dye residual rate (%) = Fatigue bleach-fix solution treatment/new bleach-fix solution treatment x 100

[Table] It is understood from Table 4 that the samples using the phenolic cyan coupler according to the present invention show less fading of the cyan dye when treated with a fatigue bleach-fix solution. Example (5) The phenolic cyan coupler of the present invention as shown in Table 5, the comparative coupler [D], and the following comparative couplers [E] and [F] were prepared in the same manner as in Example (3). , exposure, and development to obtain a sample. (Sample numbers [42] to [47]) Using this sample,
The cyan dye image was tested for light resistance, heat resistance, and moisture resistance under the same conditions as in Example (2). The results obtained are shown in Table 5.

【table】

Table 5 shows that the samples using the phenolic cyan coupler according to the present invention have excellent performance in terms of light resistance, heat resistance, and moisture resistance.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer provided on a support, at least one of the silver halide emulsion layers has the following general formula []. A silver halide photographic material containing the following phenolic cyan coupler. General formula [] [In the formula, Ar represents at least one substituent selected from a halogen atom, an alkyl group, an alkoxy group, an acyloxy group, a hydroxycarbonyl group, an alkylthio group, an alkylsulfonyl group, an acylamino group, a sulfamide group, and a carbamoyl group at the ortho position or Represents a phenyl group at the para position. X represents an oxygen atom or a sulfur atom. R
represents an alkylene group. Y represents a halogen atom. n represents an integer of 1 or 2. However, n
When is 2, Y may be the same or different. Z represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. ] However, the cyan coupler and Except when only [X represents H, ^COOR3 , an alkoxy group, a halogen atom, ^R1 , ^R2 , ^R3 each represents an alkyl group having 1 to 20 carbon atoms] is used as a solvent for the cyan coupler.