JPH0310290B2 - - Google Patents

Description

[Detailed description of the invention]

<Technical Field> The present invention relates to a silver halide color photographic light-sensitive material, and relates to a silver halide color photographic light-sensitive material that exhibits particularly good spectral absorption characteristics and provides a cyan dye image with no dye loss even when using a bleaching bath or a bleach-fixing bath that is tired from running. This invention relates to silver color photographic materials. <Prior art and its problems> Usually, in silver halide color photographic materials, exposed silver halide grains are
The oxidized product of the color developing agent produced at this time and yellow,
A dye image can be obtained by coupling with couplers that form magenta and cyan dyes. The couplers widely used to form the cyan dye are phenolic and naphthol cyan couplers. In recent years, in the photographic industry, with the rapid development of color photography, the amount of color negative film to be processed has become enormous, and a phenomenon has arisen in which the bleach bath or bleach-fix bath becomes fatigued by running. Naphthol compounds, which have been widely used as cyan couplers for color negative films, have the disadvantage that when processed in a tired bleach bath or bleach-fix bath, the dye that has been formed returns to the leuco form, causing dye loss. discovered. In order to improve these shortcomings,
-21139 publication, 56-65134 publication, 57-
Publication No. 204543, Publication No. 57-204544, Publication No. 57-
Publication No. 204545, Publication No. 58-98731, Publication No. 58-
As described in Publication No. 187928, cyan couplers having a phenylureido group at the 2-position of the phenol were developed, which dramatically improved dye loss. In terms of absorption characteristics, since the maximum absorption wavelength is relatively short compared to naphthol couplers, absorption in the green light region on the short wavelength side is large, which is disadvantageous in terms of color reproduction. Especially green light
This is the most sensitive part of human visual acuity, and even a small reduction in unnecessary absorption will bring about a significant visual improvement, so further improvements have been desired. OBJECTS OF THE INVENTION A first object of the present invention is to provide a silver halide color photographic light-sensitive material that has good spectral absorption characteristics and provides a relatively long wavelength cyan dye image. A second object of the present invention is to provide a silver halide color photographic material that provides a cyan image without dye loss even when using a bleach bath or a bleach-fix bath that is fatigued by running. A third object of the present invention is to provide a silver halide color photographic light-sensitive material having a cyan image with high sensitivity and high color density. A fourth object of the present invention is to provide a silver halide color photographic material having a cyan image that can be manufactured at relatively low cost. A fifth object of the present invention is to provide a silver halide color photographic material that provides a cyan image with excellent dispersion stability. The above object of the present invention was achieved by containing a photographic cyan coupler represented by the following general formula [] in a photosensitive emulsion layer. General formula []: [However, in this general formula, R ¹ is (However, Y is -O-, -S- or -SO ₂ -, R ⁴
teeth

[Formula] (R ⁶ is an alkyl group), R ⁵ is a hydroxy group, an alkyl group having 1 to 20 carbon atoms, or an arylsulfonyl group, 1 is an integer of 1 to 4, and 1 is an integer of 1 to 4.
When is 2 or more, R ⁵ may be the same or different. ), R ² and R ³ represent a hydrogen atom or a halogen atom, Z represents a hydrogen atom, or a group that can be eliminated during a coupling reaction with an oxidation product of a color former and a developing agent, and R ² and at least one of R ³ is a halogen atom. ] Specific description of the invention In the present invention, in R ¹ in the general formula [ ],
^R6 , which is a substituent of the methylene group constituting ^R4 , is
Examples include ethyl group, propyl group, butyl group, and the like. In addition to the hydroxy group, R ⁵ has 1 to 1 carbon atoms.
20 alkyl groups (e.g. methyl, ethyl,
tert-butyl group, tert-pentyl group, cyclopentyl group, tert-octyl group, pentadecyl group, etc.)
That's fine. The total number of carbon atoms in R ⁴ and R ⁵ is 8
-25 is preferred. l represents an integer of 1 to 4, preferably 1 or 2. In the present invention, Z in the above general formula [] represents a hydrogen atom or a group that can be eliminated during a coupling reaction with an oxidation product of a color developing agent, but such groups are well known to those skilled in the art. ing. These groups can also control the reactivity of the coupler and, after leaving the coupler, perform functions such as development inhibition, bleach inhibition, bleach acceleration, color correction, etc., thereby improving the white layer or other properties. layers can be advantageously influenced. Typical examples of these groups include halogen atoms (chloro atom, fluorine atom, etc.), alkoxy groups (methoxyethylaminocarbonylmethoxy group, methanesulfonylethoxy group, etc.), aryloxy groups (p-ethoxycarbonylphenoxy group, p-methoxyphenoxy group, p-butanesulfonamidophenoxy group, p-β-carboxypropanamidophenoxy group, etc.), arylthio group (o-bitoxyphenylthio group, p-tertbutylphenylphenoxy group, etc.) ruthio group, m-butanesulfonamidophenylthio group, etc.). Such a group that leaves during coupling is described, for example, in US Pat. No. 2,455,169.
No.;3227551;3432521;3476563;3617291
Nos. 3880661, 4052212 and 4134766, and British Patent and Patent Application Publication No.
It is described in the specifications of No. 1466728; No. 1531927; No. 1533039; No. 2006755 and No. 2017704. In the present invention, R ² and
R ³ represents a hydrogen atom or a halogen atom,
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like, with a chlorine atom being preferred. Typical examples of the cyan coupler of the present invention are described below, but the present invention is not limited thereto.

【table】

【table】

【table】

[Color developer composition]

2-Amino-5-(N-ethyl-N-β-hydroxyethylamino)-toluene sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotri Acetic 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 glacial acetic acid 10.0ml Add water to make 1, use ammonia water,
Adjust to PH6.0. [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.

[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 Hydrosulfite 5g Add water to make 1. The maximum color density of the obtained sample was measured. The results are shown in Table 2. Incidentally, the dye residual rate at the maximum density was determined as follows. Dye residual rate = fatigued bleach-fix solution processing concentration / new bleach-fix solution processing concentration x 100

[Table] As shown in Table 2, the samples using the naphthol coupler (C-1) showed significant fading of the cyan dye when treated with a fatigue bleach-fix solution, but the samples using the couplers according to the present invention (No. 18 to 22) is the comparison coupler (A) ~
It can be seen that, like the sample using (G), there is little fading of the cyan dye. Example 3 On a subbed transparent polyester base,
The following layers were sequentially installed from the support side to produce each sample having the structure shown in Table 3 below. 1st layer (antihalation layer): A gelatin aqueous solution containing black colloidal silver is mixed with 0.5 silver.
It was applied at a rate of g/m ² to a dry film thickness of 3.0 μm. Second layer (intermediate layer): An aqueous gelatin solution was coated to a dry film thickness of 1.0 μm. Third layer (red-sensitive, low-sensitivity silver halide emulsion layer): Silver iodobromide emulsion (average grain size 0.6μ, silver iodide 4
Silver iodobromide emulsion containing mol% and average grain size
Silver iodobromide emulsion containing 0.3μ, 4 mol% silver iodide:
1) was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-
Ethyl-3,3'-di-(3-sulfopropyl)-
4,5,4',5'-dibenzothiacarbocyanine hydroxide: anhydrous 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfobutyl)thiacarbocyanine hydroxide: and anhydrous 2 -[2-
{(5-chloro-3-ethyl-2(3H)-benzothiazoliden)methyl}-1-butenyl-5-chloro-3-(4-sulfobutyl)] After adding benzoxazolium, 4- Hydroxy-6-methyl-1,3,3a,7-tetrazaindene 1.0g, 1
-Phenyl-5-mercaptotetrazole 20.0mg
was added to obtain a red-sensitive low-sensitivity emulsion. Next, the cyan coupler, DIR compound, colored cyan coupler, anti-capri agent, and high-boiling solvent were added to 150 ml of ethyl acetate, dissolved by heating, and 5 g of sodium triisopropylnaphthalene sulfonate was added.
The mixture was added to 550 ml of a 7.5% aqueous gelatin solution containing the following ingredients and emulsified and dispersed using a colloid mill. After the dispersion was heated to remove ethyl acetate, the red-sensitive low-sensitivity emulsion was added thereto and coated to give a dry film thickness of 4.0 μm (containing 100 g of gelatin per mole of silver halide). 4th layer (red-sensitive high-sensitivity silver halide emulsion layer): Silver iodobromide emulsion (average grain size 1.2μ, silver iodide 7
mol %) with gold and sulfur sensitizers, and then anhydrous 9-ethyl-
3,3'-di-(3-sulfopropyl)-4,5,
4',5'-dibenzodithiacarbocyanine hydroxide; anhydrous 3,3'-dichloro-9-ethyl-3,
3'-di-(3sulfobutyl)thiacarbocyanine hydroxide: and anhydrous 2-[2-{(5-chloro-3-ethyl-2(3H)-benzothiazolidene)
methyl}-1-butenyl-5-chloro-3-(4-
sulfobutyl)} After adding benzoxazolium, 4-hydroxy-6-methyl-1,3,
1.0 g of 3a,7-tetrazyten and 10.0 mg of 1-phenyl-5-mercaptotetrazole were added to obtain a red-sensitive emulsion. Furthermore, cyan coupler, DIR compound, anti-capri agent and high boiling point solvent were added to 60 ml of ethyl acetate and dissolved by heating, followed by a 7.5% aqueous gelatin solution containing 1.5 g of sodium triisopropylnaphthalene sulfonate.
The above red-sensitive high-sensitivity emulsion was added to the dispersion which was emulsified and dispersed in 30 ml using a colloid mill, and coated to a dry film thickness of 2.0 μm (containing 100 g of gelatin per mole of silver halide). ). 5th layer (middle layer): Same as 2nd layer. 6th layer (green-sensitive, low-sensitivity silver halide emulsion layer): A silver iodobromide emulsion with an average grain size of 0.6 μ and containing 4 mol % of silver iodide and an iodine emulsion with an average grain size of 0.3 μ and containing 7 mol % of silver The silver bromide emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-ethyl-3,3'-di-
(3-Sulfobutyl)oxacarbocyanine hydroxide: anhydrous 3,3'-diphenyl-9-ethyl-3,3'-di-(3-sulfobutyl)oxacarbocyanine hydroxide; and anhydrous 9-ethyl-3,3 '-di-(3-sulfopropyl)-5,6,
Add 5',6'-dibenzoxacarbocyanine hydroxide followed by 1.0 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole.
20.0 mg was added and adjusted in the usual manner. The two types of silver halide emulsions obtained in this way were mixed in a ratio of 1:1.
A green-sensitive silver halide emulsion was obtained. Furthermore, magenta coupler, DIR coupler, colored magenta coupler, anti-capri agent, and high boiling point solvent were added to 240 ml of ethyl acetate, dissolved by heating, added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate, and placed in a colloid mill. The above green-sensitive low-sensitivity emulsion was added to the emulsified dispersion and coated to give a dry film thickness of 4.0 μm (containing 100 g of gelatin per mole of silver halide). 7th layer (green sensitive silver gelatin emulsion layer): Silver iodobromide emulsion (average grain size 1.2μ, silver iodide 7
mol %) with gold and sulfur sensitizers, and then anhydrous 5,5'-di-
Chloro-9-ethyl-3,3'-di-(3-sulfobutyl)oxacarbocyanine hydroxide; Anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfobutyl)oxacarbo cyanine hydroxide; and anhydrous 9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide;
Then 4-hydroxy-6-methyl-1,3,
1.0 g of 3a,7-tetrazyden and 10.0 mg of 1-phenyl-5-mercaptotetrazole were added to obtain a green-sensitive and highly sensitive silver halide emulsion. Furthermore, magenta coupler, DIR coupler, colored magenta coupler, anti-capri agent, and high boiling point solvent were added to 200 ml of ethyl acetate, dissolved by heating, added to a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and placed in a colloid mill. The above-mentioned green-sensitive high-sensitivity emulsion was added to the emulsified dispersion and coated to a dry film thickness of 2.0 μm (containing 100 g of gelatin per mole of silver halide). 8th layer (middle layer): Same as 2nd layer. 9th layer (yellow filter layer): 2,3-di-t-octylhydroquinone 3 in an aqueous gelatin solution in which yellow colloidal silver is dispersed.
g and 1.5 g of di-2-ethylhexyl phthalate were dissolved in 10 ml of ethyl acetate, and a dispersion prepared by dispersing the solution in an aqueous gelatin solution containing 0.3 g of sodium triisopropylnaphthalene sulfonate was added ^. , 5-di-t-octylhydroquinone was applied at a rate of 0.10 g/m ² to give a dry film thickness of 1.2 μm. 10th layer (blue-sensitive, low-sensitivity silver halide emulsion layer): Silver iodobromide emulsion (average grain size 0.6μ, silver iodide 6)
(containing mol %) with gold and sulfur sensitizers, further adding anhydrous 5,5′-dimethoxy-3,3′-di(3-sulfopropyl)thiacyanine hydroxide as a sensitizing dye, Then 4-hydroxy-
1.0 g of 6-methyl-1,3,3a,7-tetrazaindene and 20.0 mg of 1-phenyl-5-mercaptotetrazole were added and adjusted in a conventional manner to prepare a blue-sensitive, low-sensitivity silver halide emulsion. Furthermore, a yellow coupler and a high boiling point solvent were added to 300 ml of ethyl acetate, dissolved by heating, added to a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill. A low-speed emulsion was added and coated to give a dry film thickness of 4.0 microns (containing 240 g of gelatin per mole of silver halide). 11th layer (blue-sensitive high-sensitivity silver halide emulsion layer): Silver iodobromide emulsion (average grain size 1.2μ, silver iodide 7
(containing mol%) was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dimethoxy-3,3'-di-(3-sulfopropyl) thiacyanine hydroxide was added as a sensitizing dye. Then, 1.0 g of 4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene and 10.0 mg of 1-phenyl-5-mercaptotetrazole were added and adjusted in a conventional manner, and blue-sensitive high-sensitivity halogenated A silver emulsion was prepared. Furthermore, a yellow coupler and a high boiling point solvent were added to 240 ml of ethyl acetate, dissolved by heating, added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill. A high-sensitivity emulsion was added and coated to give a dry film thickness of 2.0 μm (containing 160 g of gelatin per mole of silver halide). 12th layer (intermediate layer): A high-boiling solvent and a UV image absorber were added to 2 ml of ethyl acetate, added to a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalenesulfonate, and emulsified and dispersed using a colloid mill. Add this to gelatin 1.0
It was applied at a rate of g/m ² to a dry film thickness of 1.0 μm. Thirteenth layer (protective layer): An aqueous gelatin solution containing 4 g of gelatin and 0.2 g of 1,2-bisvinylsulfonylethane per 100 ml was applied at a rate of 1.3 g/m ² of gelatin to give a dry film thickness of 1.2 μm.

[Table] In Table 3, the amount added is the amount added per mole of silver halide, and the amount of coupler, DIR coupler, and colored coupler is expressed in mol%, and the amount of addition is shown in mol% of the amount of high boiling point solvent,
The antifoggant is expressed as a weight percent based on the amount of coupler, the ultraviolet absorber is expressed as a weight per ^m2 , and the high-boiling solvent used in the 12th layer is expressed as the same weight (g) as the ultraviolet absorber ( ^m2 ).
hit) was used. Further, the antifoggant used in the fifth layer is expressed in weight (g) per m ² , and the high boiling point solvent was used in the same weight as the antifoggant. As a result of processing each sample obtained with the configuration shown in Table 3 in accordance with the processing steps shown in Example 1, it was found that the material was a silver halide color photographic light-sensitive material having stable color balance. Example 4 The spectral absorption characteristics of each dye of C-1 obtained with sample Nos. 1, 2, and 8 obtained in Example-1, comparative couplers (A), and (6) are shown in the drawing. From this figure, it can be seen that the dye formed by the coupler (6) of the present invention has a maximum absorption wavelength at a long wavelength and has good sharpness on the short wavelength side, and is a preferable dye in terms of color reproduction.

[Brief explanation of the drawing]

The drawing is a graph showing the spectral absorption characteristics of dyes formed by various couplers.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material, characterized in that a photographic cyan coupler represented by the following general formula [] is contained in a light-sensitive emulsion layer. General formula []: [However, in this general formula, R ¹ is (However, Y is -O-, -S- or -SO ₂ -, R ⁴
is [Formula] (R ⁶ is an alkyl group), R ⁵ is a hydroxy group, an alkyl group having 1 to 20 carbon atoms, or an arylsulfonyl group, 1 is an integer of 1 to 4, and 1 is an integer of 1 to 4.
When is 2 or more, R ⁵ may be the same or different. ), R ² and R ³ represent a hydrogen atom or a halogen atom, Z represents a hydrogen atom, or a group that can be eliminated during a coupling reaction with an oxidation product of a color developing agent, and R ² and At least one of R ³ is a halogen atom. ]