JPH0251492B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photographic light-sensitive material that prevents color staining, and more particularly to a silver halide color photographic light-sensitive material containing a sulfonamide phenol derivative as a color stain preventive agent. In a multilayer color photographic material containing a color-forming coupler in a silver halide photographic emulsion and developed using a color developer such as paraphenylene diamine, the oxidized color developer generated during development is It is well known that so-called "color-mixing" development occurs in which undesired dyes migrate into adjacent imaging layers. It is also known that during color development, an undesirable "color fog" phenomenon occurs due to air oxidation of the developing agent, emulsion fog, etc. In the following, this "color turbidity" and "color fog" will be collectively referred to as "color contamination." In order to prevent color staining, various methods using hydroquinone have been proposed. for example,
Regarding the use of monolinear alkylhydroquinone, US Pat.
No. 106329, and the use of monobranched alkylhydroquinones, U.S. Pat.
No. 3700453, West German Patent Publication No. 2149789, Japanese Patent Publication No. 1973-
It is described in No. 156438 and No. 49-106329. On the other hand, regarding dilinear alkylhydroquinone, US Patent No. 2728659, US Patent No. 2732300, British Patent No. 752146
No. 1086208 and "Chemical Abstract"
Journal, Vol. 58, 6367h, etc., and about di-branched alkylhydroquinone, U.S. Patent No. 3700453,
No. 2732300, British Patent No. 1086208, the above-mentioned "Chemical Abstracts" magazine, JP-A-50-156438,
It is described in Special Publication No. 50-21249, No. 56-40818, etc. In addition, regarding the use of alkylhydroquinone as a color stain prevention agent, British Patent No. 558258
No. 557750 (corresponding U.S. Patent No. 2360290);
No. 557802, No. 731301 (corresponding U.S. Patent No. 2701197)
), U.S. Patent No. 2336327, U.S. Patent No. 2403721, U.S. Patent No.
No. 3582333, West German Patent Publication No. 2505016 (corresponding Japanese patent publication No. 2505016)
50-110337) and Special Publication No. 56-40816. It is known that "color turbidity" phenomenon occurs in color diffusion transfer photographic materials as well as in ordinary color photographic materials, and the above-mentioned hydroquinones are used to prevent this phenomenon. Hydroquinone used as an agent for preventing color turbidity in diffusion transfer sensitive materials is described in JP-A-58-21249. Regarding the use of sulfonamide phenols as color turbidity preventive agents for diffusion transfer sensitive materials, see Research Disclosure, 15162 (1973), 83.
Page, JP-A-55-72158 and JP-A-57-24941 (corresponding US Pat. No. 4,366,226). In recent years, in the field of manufacturing technology for color photographic materials, in order to obtain higher quality color photographs, color contamination can be more efficiently prevented without reducing photographic sensitivity, and thinning can be used to improve sharpness. A new color stain inhibitor that can be added to layered photosensitive materials, does not cause any change in performance even after long-term storage, and also contributes to improving the light fastness of dye images formed by color development. Development is strongly desired. The first object of the present invention is to provide a new color stain inhibitor. A second object of the present invention is to provide a novel color stain prevention agent that efficiently removes oxidized products of color developers or charge transfer black developers.
A third object of the present invention is to provide a novel color stain preventive agent that can be used to form thin-layered photosensitive materials. A fourth object of the present invention is to provide a new color stain inhibitor that does not cause any change in performance even after long-term storage. Another object of the present invention is to provide a color photographic material containing this novel color stain inhibitor. The above purpose is to incorporate a repeating unit represented by the following general formula () and/or a polymer or copolymer containing a repeating unit represented by the general formula () into a silver halide color photographic light-sensitive material. This is achieved by In the formula, A and B are each -SO ₂ - or -CO-
, and at least one of A and B is -
SO ₂ -. R ¹ is a hydrogen atom, a halogen atom (fluorine, chlorine,
bromine, etc.), substituted or unsubstituted alkyl groups (which may be substituted with halogen atoms, etc.), preferably those having 1 to 20 carbon atoms. For example, methyl group, t-butyl group, cyclohexyl group, n-pentadecyl group groups), alkoxy groups (which may be substituted with halogen atoms, etc., preferably those having 1 to 20 carbon atoms; for example, methoxy groups, n-butoxy groups, etc.), arylsulfonamide groups (aryl groups are alkyl groups, It may be further substituted with an alkoxy group, etc. Those having a total number of carbon atoms of 6 to 30 are preferable. For example, 4-(n-dodecyloxy)
benzenesulfonamide group, p-tolylsulfonamide group, etc.), alkylsulfonamide group (the alkyl group may be substituted with a halogen atom or a hydroxyl group. Those having 1 to 20 carbon atoms are preferable. For example, methanesulfonamide group , n-octanesulfonamide group, etc.), an acylamino group (which may be further substituted with an alkoxy group, an aryloxy group, an alkyl group, etc.), and those having a total number of carbon atoms of 2 to 30 are preferable. For example, an acetylamino group, a benzoylamino group group, α-(2,4-di-t-amylphenoxy)propanamide group, etc.), an alkylthio group (which may be substituted with a halogen atom, etc.).
Those having 1 to 20 carbon atoms are preferred. For example, methylthio group, hexadecylthio group, etc.), arylthio group (aryl group may be further substituted with an alkyl group or alkoxy group, etc., for example, phenylthio group, 4-butoxyphenylthio group, etc.),
Heterocyclic thio group (preferably a 5- to 6-membered heterocyclic ring. The heterocyclic ring may be further substituted with an alkyl group, an aryl group, etc.) A group having a total of 1 to 20 carbon atoms is preferable. For example, 1-phenyl tetrazol-5-ylthio group), alkoxycarbonyl group (the alkyl group may be substituted with a halogen atom, etc.), and those having 2 to 20 carbon atoms are preferred.
For example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (aryl group may be further substituted with an alkyl group or alkoxy group, etc.) Those with a total number of carbon atoms of 7 to 30 are preferable. (enoxycarbonyl group, etc.), sulfamoylamino group (sulfamoyl group may be further substituted with an alkyl group, aryl group, etc.) Those with a total number of carbon atoms of 0 to 20 are preferable. For example, N,N-dipropyl (sulfamoylamino group, etc.), alkoxycarbonylamino group (preferably one with 2 to 20 carbon atoms, e.g. ethoxycarbonylamino group, butoxycarbonylamino group, etc.), carbamoylamino group (carbamoyl group is an alkyl group, aryl group, etc.) Preferably, the total number of carbon atoms is 1 to 20 (for example, N-phenylcarbamoylamino group), an acyl group (preferably 2 to 20 carbon atoms),
20. For example, acetyl group, ethylcarbonyl group, etc.), sulfonyl group (preferably 1 to 30 carbon atoms).
For example, a benzenesulfonyl group), a carbamoyl group (which may be substituted with an alkyl group, an aryl group, etc.), preferably having 0 to 20 carbon atoms. For example, N-
phenylcarbamoyl group, N,N-dioctylcarbamoyl group, etc.). R ² and R ³ each represent a substituted or unsubstituted aryl group (the aryl group may be further substituted with a halogen atom, an alkyl group, an alkoxy group, etc.) having a total number of carbon atoms of 6 to 30; Preferred. For example, 4-(n-dodecyloxy)phenyl group, p-tolyl group, 3,4-dichlorophenyl group, 4-dodecylphenyl group, etc.), alkyl group (alkyl group is halogen atom, hydroxyl group, aryloxy group, alkoxy group) It may be substituted with etc. Those having a total number of carbon atoms of 1 to 30 are preferable. For example, methyl group, trifluoromethyl group, n
-hexadecyl group, 1-(m-pentadecylphenoxy)propyl group, etc.), amino group (amino group may be substituted with an alkyl group, aryl group, etc.) having a total number of carbon atoms of 0 to 30. Preferred. For example, dimethylamino group, dipropylamino group, etc.). R ² and R ³ may be the same or different. _R4 is

【formula】

【formula】

【formula】

【formula】

[Formula] - CH ₂ CH ₂ O -,

【formula】

[Formula] represents ―NHCH ₂ CH ₂ NHCO―, and R ₅ is

【formula】

【formula】

【formula】

[Formula] ―CH ₂ CH ₂ CH ₂ NHCO―, ―NHSO ₂ ―,

【formula】

[Formula] represents. R ₆ is a hydrogen atom, a halogen atom (fluorine, chlorine,
bromine, etc.), alkyl groups (preferably 1 to 1 carbon atoms),
6 things. For example, methyl group, ethyl group, etc.). n is 0 or 1. The substituents on the phenol ring in the general formula () or () may be substituted at any position on the ring. Among those represented by the general formula () or (), those represented by the general formula () are preferred. Among the repeating units represented by the general formula (), those represented by the following general formula are preferred. A, B in these general formulas () to (),
R ¹ to R ⁶ and n are the same as defined in the general formula (). In the general formulas () to (), R ¹ is
In the case of () and (), hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, alkoxycarbonyl group, arylthio group,
Preferably, they are a heterocyclic thio group, an aryloxycarbonyl group, an acyl group, a sulfonyl group, or a carbamoyl group. In the case of () to (), R ¹ is a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, a sulfamoylamino group, a carbamoylamino group, an acyl group, It is preferably a carbamoyl group, especially a group that does not cause color development due to oxidative coupling with a color developing agent in color development (alkyl group, alkoxycarbonyl group, sulfonyl group, aryloxycarbonyl group, acyl group, carbamoyl group). is preferred. Among the repeating units represented by the general formulas () to (), those represented by the general formulas () to () are preferable. It is particularly preferable that R ² and R ³ in the general formulas () to () are an aryl group or an alkyl group. It is particularly preferable that A and B in the general formulas () to () are both -SO ₂ -. Among the general formulas () to (), the most preferable one is the general formula () or (). The polymer or copolymer used in the present invention may consist only of repeating units of the general formula () or (), or may be a copolymer consisting of repeating units of both general formulas () and (). , and the repeating unit of the general formula () and/or () and the general formula () or ()
It may also be a copolymer containing repeating units other than the above. Such polymers or copolymers generally include homopolymerization of monomers capable of deriving repeating units of general formula () or (), or polymerization of monomers capable of deriving repeating units of general formula () and (). It can be obtained by copolymerization or copolymerization of these monomers with other ethylenically unsaturated monomers capable of addition polymerization. Specific examples of monomers from which the repeating unit of general formula () or () can be derived are listed below, but the present invention is not limited thereto. Other ethylenically unsaturated monomers that can be addition-polymerized with monomers that can induce repeating units of general formula () or () include polymerization temperature (generally 50°C).
In principle, all water-insoluble monomers which are liquid at temperatures between ~95[deg.]C and preferably between 70[deg.]C and 90[deg.]C can be used. Specifically, for example, acrylic acid, α-chloroacrylic acid, α-alacrylic acid (methacrylic acid, etc.)
esters or amides derived from acrylic acids such as t-butylacrylamide,
Methyl acrylate, methyl methacrylate,
Ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate,
n-hexyl acrylate, octyl methacrylate, etc.), vinyl esters (e.g. vinyl acetate, acrylonitrile, etc.), aromatic vinyl compounds (e.g. styrene, vinyl toluene,
divinylbenzene, etc.), vinyl alkyl ethers (e.g. vinylthyl ether, maleic acid ester, etc.). Examples of the composition of the polymer or copolymer according to the present invention are shown below, but the present invention is not limited thereto. Monomers from which repeating units of general formula () or () can be derived are generally synthesized by an amidation reaction between a sulfonamide-substituted aminophenol and an ethylenically unsaturated monomer having an acid halide residue. be able to. Next, examples of synthesis of monomers used in the present invention will be shown. Synthesis example 1 Synthesis of exemplified compound (1) Dissolve aniline (A) (15.4 g) in 80 ml of pyridine, stir, and add solid sulfonyl chloride (B).
(36.1g) was added. A slight exotherm was observed.
The mixture was heated at reflux temperature for 1 hour and then allowed to cool for 10 minutes. Then 500ml of ice water containing 100ml of concentrated hydrochloric acid.
The mixture was slowly poured onto the mixture while stirring. The precipitated crystals were collected, washed with water, and dried to obtain 47 g of yellow crystals (C). Nitrophenol (C) (47 g) and reduced iron (25 g) were placed in 200 ml of isopropanol, and heated to reflux while stirring. Then, 10 ml of concentrated hydrochloric acid was gradually added dropwise, and after stirring for 30 minutes, the mixture was allowed to cool, and 300 ml of ethyl acetate and 300 ml of 5% aqueous sodium bicarbonate were added to remove the solid content. The ethyl acetate layer was separated, washed with water, and then concentrated to obtain dark brown crude crystals. After treatment with activated carbon, the crystals were recrystallized from methanol to obtain 39 g of light brown crystals (D). Aniline (D) (22.4 g) and nitrobenzene (1 ml) were dissolved and stirred in 80 ml of pyridine, and sulfonyl chloride (E) (10.1 g) was added thereto. This mixture was heated at 60° C. for 1 hour and then allowed to cool for 10 minutes. The mixture was then slowly poured onto 500 ml of ice water containing 100 ml of concentrated hydrochloric acid while stirring. The precipitated crystals were collected, washed with water, dried, and purified to obtain 19 g of pale brown crystals (F). Calculated value as C ₃₂ H ₄₂ N ₂ O ₆ Os C; 62.51 H; 6.88 N; 4.56 Actual value C; 62.30 H; 6.69 N; 4.48 Next, a synthesis example of the polymer or copolymer used in the present invention is shown. show. Synthesis example 2 Synthesis of exemplified compound (b) 30 g of exemplified compound (22) and 10 butyl acrylate
Dissolve g in 200 ml of dioxane. After raising the temperature of the system to 70°C, 0.4 g of methyl azobisisobutyrate was added. After stirring for 1 hour, 0.4 g of methyl azobisisobutyrate was further added. After stirring for 1 hour, 0.4 g of methyl azobisisobutyrate was further added, the temperature was raised to 100°C, and the mixture was stirred for 1 hour. After cooling, the system was added dropwise to ice water 2, taken out, and dried to obtain 37 g of a white polymer. When the polymer or copolymer of the present invention is used as a color turbidity preventive agent in an intermediate layer, the equivalent of the sulfonamide phenol residue in the repeating unit represented by the general formula () or () is 1.0×10 per layer. ^-3 ～
It is preferably used at a concentration of 1.0×10 ^-5 mol/m ² , and when used in the emulsion layer as a color antifoggant,
It is preferable to use 1.0×10 ⁻⁴ to 1.0×10 ⁻⁶ mol/m ² per layer, but the amount is not limited thereto.
Furthermore, it can be added to both the intermediate layer and the emulsion layer to prevent color turbidity and color fog. The polymer or copolymer of the present invention can contain a high concentration of sulfonamide phenol residue, and the viscosity of an aqueous gelatin solution does not increase much, so that it is suitable for forming a thin-layered sensitive material. The polymer or copolymer of the invention is preferably dispersed in water, in the form of a so-called polymer latex, and is added to a coating solution (often an aqueous gelatin solution) and coated. In order to introduce the compound of the present invention into constituent layers such as emulsion layers and interlayers, known methods used for introducing couplers into emulsion layers can be applied. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate),
Citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (such as tributyl trimesate), or boiling point approximately 30
organic solvents such as ethyl acetate,
After a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. are dissolved, they are dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. The color stain preventive agent of the present invention is a type that forms a color image through oxidative coupling between an aromatic primary amine developer (for example, a phenylene diamine derivative or an aminophenol derivative) and a color-forming coupler in color development processing. It is highly effective in preventing color staining of silver halide color photographic materials (for example, color paper, color negative film, color reversal film, etc.). Color-forming couplers used in this type of color photographic material include, for example, magenta couplers such as 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, and yellow couplers such as acylacetonitrile couplers. Examples include acetamide couplers (eg, benzoylacetanilides, pivaloylacetanilides), and cyan couplers include thiphthol couplers and phenol couplers. These couplers are preferably used because they can be made non-diffusive by introducing a hydrophobic group called a ballast group into the molecule or by bonding them to a polymer chain. The coupler is 4-equivalent or 2-equivalent to silver ion.
Either equivalence is acceptable. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). A specific example of a magenta coloring coupler is a U.S. patent
No. 2600788, No. 2983608, No. 3062653, No.
No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558319, No. 3582322, No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 51-20826, No. 52-58922
No. 49-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74028, No. 50
-60233, No. 51-26541, No. 53-55122, etc. A specific example of a yellow coupler is U.S. Patent No. 2875057.
No. 3265506, No. 3408194, No. 3551155,
3582322, 3725072, 3891445, West German Patent No. 1547868, West German Patent Application No. 2219917,
No. 2261361, No. 2414006, British Patent No. 1425020,
Special Publication No. 51-10783, Japanese Patent Publication No. 47-26133, No. 48-
No. 73147, No. 51-102636, No. 50-6341, No. 50
−123342, No. 50-130442, No. 51-21827,
These are described in No. 50-87650, No. 52-82424, No. 52-115219, etc. Specific examples of cyan couplers are U.S. Patent No. 2369929,
Same No. 2434272, No. 2474293, No. 2521908, Same No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
No. 3591383, No. 3767411, No. 4004929, West German patent application (OLS) No. 2414830, No. 2454329, Japanese Patent Application Publication No. 48-59838, No. 51-26034, No. 48-5055,
These are those described in No. 51-146828, No. 52-69624, and No. 52-90932. As a colored coupler, for example, a US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, JP-A No. 51-26034, No. 52-
Specification No. 42121, West German Patent Application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, Japanese Patent Application Publication No. 1983-69624, No. 49-122335
Those described in Japanese Patent Publication No. 51-16141 can be used. The color stain inhibitor of the present invention is also useful for preventing color stains in so-called diffusion transfer type silver halide color photographic light-sensitive materials. Examples of dye image-forming compounds used in this type of sensitive material include dye developers,
There are dye-releasing redox compounds, DDR couplers, etc., specifically, for example, US Pat. No. 4,053,312;
Same No. 4055428, No. 4076529, No. 4152153, Same No.
No. 4135929, Japanese Patent Publication No. 53-149328, No. 51-104343
No. 53-46730, No. 54-130122, No. 53-
No. 3819, Patent Application No. 54-89128, No. 54-90806,
No. 54-91187, etc. can be used. The compound of the present invention may be used in combination with known color stain inhibitors, such as hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like. Specific examples are US Patent Nos. 2360290 and 2336327.
No. 2403721, No. 2418613, No. 2675314,
2701197, 2704713, 2728659, 2701197, 2704713, 2728659,
No. 2732300, No. 2735365, JP-A-50-92988,
No. 50-92989, No. 50-93928, No. 50-110337
No. 52-146235, Japanese Patent Publication No. 50-23813, etc. The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer. In addition, regarding photographic silver halide emulsions, their preparation methods, and photographic additives (or photographic materials) that can be used in the color sensitive material of the present invention, please refer to "Research Disclosure" magazine, No. 176 (1978
(November 2015) on pages 22-31 of ``Preparation and Types of Emulsions'', ``Water Washing of Emulsions'', ``Chemical Sensitization'', ``Antifoggants and Stabilizers'', ``Hardeners'', ``Supports''. ”, “Plasticizers and lubricants”, “Coating aids”, “Matting agents”, “Sensitizers”, “Spectral sensitizers”, “Methods of addition”, “Absorption and filter dyes” and “Methods of application” etc. can be applied. For color image formation, the negative-positive method (for example, “Journal of the Society of Motion Picture
and Television Engineers” Volume 61 (1953),
667-701), developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other suitable fogging treatment, followed by color development. The color reversal method, in which a dye-positive image is obtained by performing development, and the silver dye bleaching method, in which a photographic emulsion layer containing a dye is exposed and developed to form a silver image, and this is used as a bleaching catalyst to bleach the dye, etc. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (for example, 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
pages 226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. Can be done. Also, if necessary, water softener,
Preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol,
Polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers,
Competitive couplers, fogging agents such as sodium borohydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifying agents, US patents
The polycarboxylic acid chelating agent described in No. 4083723,
It may also contain antioxidants such as those described in OLS 2622950. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates;
Nitrosophenols and the like can be used.
Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. When the present invention is used in a diffusion transfer method, it can also be processed with a viscous developer. This viscous developer is a liquid composition containing processing components necessary for developing the silver halide emulsion and forming a diffusion transfer dye image, and the solvent is mainly water.
It may also contain other hydrophilic solvents such as methanol and methyl cellosolve. The processing composition maintains the pH necessary for development of the emulsion layer and removes acids generated during the development and dye image formation processes (e.g., hydrohalic acids such as hydrobromic acid, carboxylic acids such as acetic acid). Contains a sufficient amount of alkali to neutralize acids (acids, etc.). Examples of alkalis include alkali metal or alkaline earth metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, diethylamine, or amines. It is desirable to contain a caustic alkali at a concentration such that it has a pH of about 12 or higher, particularly a pH of 14 or higher at room temperature. More preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose. These polymers are preferably used to give the treatment composition a viscosity of 1 poise or more, preferably several hundred (500 to 600) to 1000 poise at room temperature. The present invention will be explained in more detail with reference to Examples below. Example 1 Film A Yellow coupler α-pivaloyl-α(2,4-dioxo-5,5′-dimethyloxazolidin-3-yl)-2 as first layer on a baryta paper support coated on both sides with polyethylene. -chloro-5
- Coating a blue-sensitive silver chlorobromide emulsion layer containing [α-(2,4-di-tert-pentylphenoxy)butanamide] acetanilide to a thickness of 3.0μ (Coating amount of coupler: 0.646×10 ^-3 mol) /m ² , coated silver amount 3.88×
10 ^-3 mol/m ² , silver bromide 70 mol%, silver chloride 30 mol%), and then a gelatin layer of 1.5μ as a second layer on top.
It was applied to a thickness of . Furthermore, magenta coupler 1-(2,
4,6-trichlorophenyl)-3-{2-chloro-(5-tetradecanamido)anilino}-5
- A gelatin layer containing pyrazolone was coated to a thickness of 3.1μ (coupler coating amount 0.500 x 10 ^-3 mol/
m ² Film B Film A is the same as Film A except that the second layer contains 2,5-dioctylhydroquinone.
Same as (hydroquinone application amount 1.59×10 ^-4 mol/
m ² ) to prepare Film B. In addition, the following films C to E were produced. Film C In the above film A, the exemplified compound (a) is used in the second layer.
Film A except that it contains 0.09g/m ² (1.59×10 ^-4 mol/m ² as sulfonamide phenol residue)
Same as. Film D In the above film A, the exemplified compound (b) is used in the second layer.
Film A except that it contains 0.106g/m ² (1.59×10 ^-4 mol/m ² as sulfonamide phere residue)
Same as. Film E In the above film A, the exemplified compound (b) is used in the second layer.
Same as film A except that it contains 0.053 g/m ² (8.0×10 ⁻⁵ mol/m ² as sulfonamide phenol residue). Films A to E produced in this way were exposed continuously through wedges with different gray densities,
The following processing was performed. Processing process Color development 3 minutes 30 seconds 33℃ Bleach-fixing 1 minute 30 seconds 33℃ Water washing 3 minutes 28-35℃ Color developer Benzyl alcohol 15ml Diethylenetriaminepentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ CO ₃ 30g Hydroxylamine sulfate 2g 4-Amino-3-methyl-N-β-(methanesulfonamide)ethylaniline 3/
2H ₂ SO ₄・H ₂ O 4.5g Make up to 1000ml with water PH10.1 Bleach-fix ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Make up to 1000ml with water PH6. 8 The density of each developed sample was measured using a green filter (magenta color density). The magenta color mixture in the yellow coloring area was investigated by determining the difference between the magenta density at the maximum yellow coloring density and the magenta density at the lowest yellow coloring density. The results are shown in the table below.

[Table] The smaller the number, the less color mixture there is. Therefore, it is clear that the compound of the present invention has excellent ability to prevent color mixing (color fog) and exhibits a sufficient effect even when added in a small amount. Example 2 Preparation of Film A Yellow coupler α-pivaloyl-α (2,
4-dioxo-5,5′-dimethyloxazolidin-3-yl)-2-chloro-5-[α-(2,4
-di-t-pentylphenoxy)butinamide]
A blue-sensitive silver chlorobromide emulsion layer containing acetanilide was coated to a dry film thickness of 3μ (coupler coating amount 0.646×
10 ^-3 mol/m ² , coating silver amount 3.88×10 ^-3 mol/m ² , the halogen composition of silver chlorobromide is 70 mol % silver bromide and 30 mol % silver chloride), and on top of that, gelatin layer
It was applied to a dry film thickness of 1μ. Films B to E Compounds of the present invention in addition to the above yellow couplers
Film B was prepared in the same manner as Film A except that 0.02×10 ^-3 mol ^* /m ² of each of (A), (B), (C), and (D) were added.
~E was produced. (*Calculated based on sulfonamide phenol residues) Each of the above films was exposed through a wedge with continuously changing gray density, and color development was performed at 38°C for 3 minutes in the process shown in Example 1. The same treatment as in Example 1 was performed. After the treatment, the yellow density was measured and the maximum density (Dmax) and minimum density (Dmin) were determined. The results are shown in the table below.

[Table] Films B to E using the compounds of the present invention have lower minimum densities than Film A, indicating that color fog is improved. The above films A to F (before exposure) were kept at a relative humidity of 50
When film A was exposed and processed in the same manner as above after being stored for 3 days at a temperature of 50°C, a decrease in maximum density and an increase in minimum density were observed for film A, whereas film B ~ In E, both the maximum and minimum concentration changes were very small. Example 3 A multilayer color (negative) light-sensitive material was prepared by providing the following layers on a cellulose triacetate film support. <1st layer anti-halation layer> (dry film thickness 2.0μ) <2nd layer low red-sensitive emulsion layer> 400 g of the following cyan coupler emulsion (1) (containing 70 g of cyan coupler and 100 g of gelatin) and the same cyan Emulsion containing a coupler and the following DIR compound (2)
(containing 70 g of cyan coupler, 10 g of DIR compound, and 100 g of gelatin), 200 c.c. of a 2% aqueous solution of the following colored cyan coupler, and 200 c.c. of a low-sensitivity red-sensitive silver iodobromide emulsion (containing 100 g of silver halide, 70 g of gelatin). (Iodine content: 5.0 mol%) was mixed to 1 kg and coated to a dry film thickness of 3.5 μm. <3rd layer Highly sensitive red-sensitive emulsion layer> 220g of emulsion (1) used in the second layer, emulsion (2)
30g, colored cyan coupler aqueous solution (2%)
200 c.c., each was mixed with 1 kg of a high-sensitivity red-sensitive silver iodobromide emulsion (5 mol % iodine content containing 100 g of silver halide and 70 g of gelatin) and coated to a dry film thickness of 2.2 μm. <4th layer gelatin intermediate layer> 2,5-di-t-octylhydroquinone 50g
dibutyl phthalate 100 c.c. and ethyl acetate 100 c.c.
700 g of the emulsion obtained by stirring and emulsifying 1 kg of a 10% gelatin aqueous solution was mixed with 1 kg of a 10% gelatin aqueous solution and coated to a dry film thickness of 1.2 μm. <5th layer low green sensitivity emulsion layer> Emulsion (3) containing 50g of the following magenta coupler and 10g of the following colored magenta coupler (gelatin 100g)
320g (including g), 50g of the same magenta coupler,
10g of the same colored magenta coupler and the following DIR
180 g of emulsion (4) containing 15 g of the compound (containing 100 g of gelatin) and a low-sensitivity green-sensitive silver iodobromide emulsion (containing 100 g of silver halide and 70 g of gelatin) were prepared.
(Iodine content: 5 mol%) 1 kg, dry film thickness
It was applied to a thickness of 3.2μ. <6th layer Highly green sensitive emulsion layer> 150g of emulsion (3) used in the second layer, emulsion (4)
30 g of each were mixed with 1 kg of a high-sensitivity green-sensitive silver iodobromide emulsion (containing 100 g of silver halide and 70 g of gelatin. Iodine content: 5 mol %) and coated to a dry film thickness of 2.2 μm. <7th Layer: Gelatin Intermediate Layer> A gelatin aqueous solution was applied to give a dry film thickness of 0.9 μm. <8th layer yellow filter layer> Dry gelatin solution containing yellow colloidal silver
It was applied to a thickness of 1μ. <9th layer low-sensitivity blue-sensitive emulsion layer> The following yellow coupler emulsion (5) (containing 100 g of yellow coupler and 100 g of gelatin) was mixed into a low-sensitivity blue-sensitive silver iodobromide emulsion (containing 100 g of silver halide and 70 g of gelatin). .Iodine content 5 mol%) 150 per kg
g was added, mixed, and coated to a dry film thickness of 3.0 μm. <10th layer Highly sensitive blue-sensitive emulsion layer> 300 g of the emulsifier (5) used in the 9th layer, a highly sensitive blue-sensitive silver iodobromide emulsion (100 g of silver halide, gelatin
Contains 70g. (Iodine content: 5 mol%) was mixed to 1 kg and coated to a dry film thickness of 2.5 μm. <11th Layer, 2nd Protective Layer> (Dry Film Thickness: 1 μm) <12th Layer: Gelatin Protective Layer> (Dry Film Thickness: 1.5 μm) The film sample thus prepared is referred to as Film A. In the above, as the emulsion of the fourth layer, 2,5
Film B was produced in the same manner except that the compound (a) ^* of the present invention was used in place of -di-t-octylhydroquinone. (*1.59×10 ^-4 mol/m ² used in terms of sulfonamide phenol residue) These samples were exposed to red light through a wedge whose gray density was continuously changed, and the following treatments were performed. . 1 Color development 3 minutes 15 seconds 2 Before bathing 30 seconds 3 Bleaching 4 minutes 20 seconds 4 Fixing 4 minutes 20 seconds 5 Washing 3 minutes 15 seconds 6 Stabilization 30 seconds The processing solution composition used in each step is as follows. It was hot. Color developer Nitrilotriacetic acid trisodium salt 1.9g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)- 2-Methylaniline sulfate 4.5g Add water 1.0 PH10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt
100.0g Ethylenediaminetetraacetic acid disodium salt 8.0g Ammonium bromide 150.0g Add water 1.0 PH6.0 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water Add 1.0 PH6.6 stabilizer formalin (40%) 8.0ml water to 1.0 Measure the density of developed films A and B using a green filter, and find the maximum color density and minimum color density (green sensitive layer). Upon investigation, it was found that the magenta color density of Film B using the compound of the present invention was lower than that of Film A, indicating that color mixing was better prevented.

Claims (1)

[Scope of Claims] 1. A silver halide color photograph characterized by containing a repeating unit represented by the following general formula () and/or a polymer or copolymer containing a repeating unit represented by the general formula (). photosensitive material. However, in the formula, A and B are respectively -CO- or -
SO ₂ -, at least one of which is -SO ₂ -. R ¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an arylsulfonamide group, an alkylsulfonamide group, an acylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonyl group, aryloxycarbonyl group, sulfamoylamino group, alkoxycarbonylamino group, carbamoylamino group, acyl group, sulfonyl group,
Represents a carbamoyl group. R ² and R ³ each represent a substituted or unsubstituted aryl group, alkyl group, or amino group, and may be the same or different.
R ₄ represents [Formula] [Formula] [Formula] [Formula] [Formula] ―CH ₂ CH ₂ O ―, [Formula] [Formula] ―NHCH ₂ CH ₂ NHCO―, and R ₅ represents [Formula] [Formula] [Formula] [Formula] -CH ₂ CH ₂ CH ₂ NHCO-, -NHSO ₂ -, [Formula] [Formula] Represents. R ₆ represents a hydrogen atom, a halogen atom, or an alkyl group. n represents 0 or 1. General formula (),
The substituents on the phenol ring in () may be substituted at any position on the ring. 2 A, B in the general formula () or () above
The color photographic material according to claim 1, wherein both are -SO ₂ -.