JPH0565864B2 - - 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 multilayer color photographic materials of the type that contain a color-forming coupler in a silver halide photographic emulsion and are developed using a color developer such as paraphenylene diamine, the oxidized product of the color developer generated during development is It is well known that the phenomenon of so-called "color turbidity" (color mixing) occurs in which undesirable dyes are formed by migrating into the image forming layer. Furthermore, it is known that during color development, an inconvenient "color fog" phenomenon occurs due to air oxidation of the developing agent, fog of the emulsion, and the like. 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, see US Pat.
No. 106329, and U.S. Patent No. 3700453 for the use of monobranched alkylhydroquinones.
No., West German Patent Publication No. 2149789, Japanese Patent Publication No. 156438
No. 49-106329. On the other hand, regarding dilinear alkylhydroquinone, the US patent
No. 2728659, No. 2732300, British Patent No. 752146, No. 2732300, British Patent No. 752146,
Issue 1086208 and "Chemical Abstract" magazine volume 58
6367h, etc., and for di-branched alkylhydroquinone, U.S. Pat.
No., British Patent No. 1086208, "Chemical Abstracts" magazine cited above, Japanese Patent Publication No. 156438-1973, Japanese Patent Publication No. 156438, Publication No. 1973
It is described in No.-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. 3582333,
West German Patent Publication No. 2505016 (corresponding Japanese Patent Publication No. 50-110337)
No.) 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. As a hydroquinone used as an agent for preventing color turbidity in diffusion transfer sensitive materials, JP-A-Sho
It is described in No. 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 a thin layer is used to improve sharpness. Development of a new color stain preventive agent that can be added to processed photosensitive materials, does not cause any changes in manufacturing even after long-term storage, and also contributes to improving the light fastness of dye images formed by color development. is strongly desired. The first object of the present invention is to provide a novel 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 objects of the present invention are achieved by incorporating a compound represented by the following general formula () which does not form a dye upon reaction with an oxidized color developing agent into a silver halide color photographic light-sensitive material as a color stain preventive agent. achieved. In the formula, R ¹ may be substituted with a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, etc.), an alkyl group (a halogen atom, a hydroxyl group, an alkoxy group, etc.), and preferably has a total number of carbon atoms of 1 to 20. such as methyl group, ethyl group, t-butyl group,
n-pentadecyl group, etc.), alkoxy groups (which may be substituted with halogen atoms, hydroxyl groups, aryl groups, etc., preferably those having a total carbon number of 1 to 20, such as methoxy groups, ethoxy groups, butoxy groups) , alkylthio group (which may be substituted with a halogen atom, hydroxyl group, alkoxy group, etc.)
Preferably, the total carbon number is 1 to 20, such as methylthio group, hexadecylthio group, etc.), alkoxycarbonyl group (alkoxy group may be substituted with a halogen atom, hydroxyl group, aryl group, etc.), and preferably has a total carbon number of 1 to 20. Numbers 2 to 20,
For example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (aryl group may be substituted with alkyl group, alkoxy group, etc., and preferably has a total number of carbon atoms of 7.
~30, such as a phenoxycarbonyl group), an acyl group (preferably one having an alkyl group or aryl group having 1 to 20 carbon atoms, such as an acetyl group or an ethyl carbonyl group), a sulfonyl group ( Preferably an alkyl group having 1 to 30 carbon atoms,
aryl group, such as p-toluenesulfonyl group), carbamoyl group (preferably an alkyl group having 1 to 20 carbon atoms, and aryl group, such as di-n-octylcarbamoyl group). R ² and R ³ are each a substituted or unsubstituted aryl group (the aryl group may be further substituted with a halogen atom, an alkyl group, an alkoxy group, etc.) and preferably have a carbon number of 6 to 30. For example, 4-(n-dodecyloxy)phenyl group, p-tolyl group, 3,4-dichlorophenyl group, 4-dodecylphenyl group, etc.), alkyl group (alkyl group is a halogen group, hydroxyl group, aryloxy group, alkoxy group, etc.) Therefore, it may be further substituted.The total number of carbon atoms is preferably 1 to 30.For example, methyl group, trifluoromethyl group, n-hexadecyl group, 1-(m-pentadecylphenoxy)propyl group, etc.) The expressions may be the same or different. One of A and B is _-SO2- and the other is -CO-. The ring substituted by the OH group may be a phenol ring, or may form a naphthol ring in conjunction with the atomic group Q. Among the compounds represented by the general formula (), the compounds represented by the following general formula () are preferred. However, R ¹ , R ² , R ³ , A and B are each the same as defined in the general formula (). In general formulas () and (), R ¹ is particularly preferably a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and most preferably a hydrogen atom. Moreover, those in which the total number of carbon atoms in R ¹ , R ² , and R ³ is 10 or more are particularly preferable because diffusion from the additive layer is small. When the compound of the present invention is used as a color turbidity preventive agent in an intermediate layer, it is used in an amount of 1.0×10 ^-3 to 1.0×10 ^-5 per layer.
It is preferably used in an amount of mol/ ^m2 , and when used as a color antifoggant in an emulsion layer, it is used in an amount of 1.0 mol/m2 per layer.
It is preferable to use the amount of x10 ^-4 to 1.0 x 10 ^-6 mol/m ² , but the amount is not limited thereto. moreover,
It can also be added to both the intermediate layer and the emulsion layer to prevent color turbidity and color fog. It can also be added to antihalation layers and protective layers. Specific examples of the compounds according to the present invention are shown below, but the present invention is not limited thereto. A specific synthesis example of the compound according to the present invention is shown below. The compound according to the present invention can be synthesized according to the general formula according to the following synthesis example. Synthesis example (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
ml of the above mixture was gradually poured onto it while stirring. The precipitated crystals were collected, washed with water, and dried to obtain 47 g of yellow crystals C. Step 2 Nitrophenol C (47 g) and reduced iron (25 g) were placed in 200 ml of isopropanol, and the mixture was heated to reflux while stirring. 10 ml of concentrated hydrochloric acid was gradually added dropwise thereto, and after stirring for 30 minutes, it was left to cool and ethyl acetate was added.
300 ml and 300 ml of 5% sodium bicarbonate solution 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. Recrystallization from activated carbon-treated methanol gave 39 g of light brown crystals D. Step 3 Aniline D (6.7 g) was dissolved in 20 ml of pyridine and stirred, and a mixture of acid anhydride E (3.2 g) and acetonitrile (10 ml) was added dropwise thereto. Heat to 80℃
After being kept for 1 hour, the system was allowed to cool, and the system was added dropwise to cold hydrochloric acid water containing 20 ml of concentrated hydrochloric acid. Take the precipitated crystals,
After washing with water and drying, the crystals were recrystallized from acetonitrile to obtain 5.2 g of pale brown crystals F. Melting point 165-7℃. Calculated value as C ₂₆ H ₃₅ F ₃ N ₂ O ₅ S ₁ C: 57.34 H: 6.48 N: 5.14 Actual value C: 57.38 H: 6.40 N: 5.01 The compound of the present invention is used in constituent layers such as emulsion layers and intermediate layers. In order to introduce the coupler into the emulsion layer, known methods used for introducing the coupler into the emulsion layer 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 with a melting point of about 30
organic solvents such as ethyl acetate,
After being dissolved in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is 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 inhibitor 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 supplement 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-pyrozolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumaron couplers, open-chain acylacetonyl tolyl couplers, and yellow couplers. Examples of the cyan couplers include acylacetamide couplers (eg, benzoylacetanilides and pivaloylacetanilides), and examples of cyan couplers include naphthol 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. 3519459, 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. 40049290, West German Patent Application (OLS) No. 2414830, No. 2454329, JP-A-Sho
No. 48-59838, No. 51-26034, No. 48-5055, No.
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. Dye image-forming compounds used in this type of sensitive material include, for example, dye developers, dye-releasing redox compounds, and DDR couplers.
No. 4055428, No. 4076529, No. 4152153,
4135929, JP 53-149328, JP 51-
No. 104343, No. 53-46730, No. 54-130122, No.
No. 53-3819, 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 prevention materials such as hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, and ascorbic acid derivatives. Specific examples are US Patent Nos. 2360290 and 2336327.
No. 2403721, No. 2418613, No. 2675314,
2701197, 2704713, 2728659, 2701197, 2704713, 2728659,
No. 2732300 No. 3 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 2013) ``Preparation and types of emulsions'', ``Washing of emulsions'', ``Chemical sensitization'', ``Antifoggants and stabilizers'', ``Hardeners'', ``Supports'' described in paragraphs 22-31 ", "Plasticizers and lubricants", "Coating aids", "Matte 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
to 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 phenylenediamines (e.g., 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-methanesulforamidoethylaniline, 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 nitrites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. can. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium borohydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, US Pat. No. 4,083,723
It may also contain a polycarboxylic acid chelating agent described in No. 1, an antioxidant described in OLS No. 2622950, and the like. 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 solutions are manufactured by U.S. Patent No.
Bleaching accelerators described in JP-A No. 3042520, JP-A No. 3241966, JP-A No. 45-8506, JP-A-45-8836, etc.;
In addition to the thiol compound described in No. 53-65732, 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)- as a first layer on a baryta paper support coated on both sides with polyethylene. 2-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 (coupling 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,
A gelatin layer containing 4,6-trichlorophenyl)-3-{2-chloro(5-tetradecanamido)anilino}-5-pyrazolone was coated to a thickness of 3.1μ (coupler coverage 0.500×10 ^-3 mol/ ^m2 ). Film B Same as film A except that the second layer contains 2,5-di-t-octylhydroquinone (hydroquinone coating amount: 1.59×10 ^-4
mol/m ² ) to prepare Film B. In addition, the following films C to E were produced. Film C The above Film A except that the second layer contains the compound (1) of the present invention at 1.59×10 ^-4 mol/m ²
Same as. Film D The above Film A except that the second layer contains 8.0×10 ^-4 mol/m ² of the compound (1) of the present invention.
Same as. Film E The above Film A except that the second layer contains the compound (4) of the present invention at 1.59×10 ^-4 mol/m ²
Same as. 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 solution Ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDAT)] 40g EDTA 4g Make up to 1000ml with water PH6.8 Each was developed The density of the 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] Mixed colors indicate that there are fewer methods with smaller values. 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-
A blue-sensitive silver chlorobromide emulsion layer containing di-t-pentylphenoxy)butynamide] acetanilide.
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
^{Films B} ~
I created E. The above films were exposed through a wedge of continuously varying gray density, and the same process as in Example 1 was carried out, except that color development was performed at 38°C for 3 minutes in the process shown in Example 1. Ta. 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 E (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 the maximum density and an increase in the minimum density were observed for film B. In E, both the maximum and minimum concentration changes were very small. Example 3 Film A A film sample was obtained by coating an emulsion layer and an auxiliary layer on a triacetyl cellulose support in the following order. <First layer: low-sensitivity red-sensitivity emulsion layer> 100 g of 2-(heptafluorobutyramide)-5-{2'-(2″,4″-di-t-amylphenoxy)butyramide}phenol, which is a cyan coupler.
was dissolved in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate, stirred and emulsified with 1 kg of 10% gelatin aqueous solution, and 500 g of the obtained emulsion was mixed with 1 kg of red-sensitive silver iodobromide emulsion (70 g (containing 60 g of gelatin and iodine content of 4.5 mol%) was mixed and coated to a dry film thickness of 2 μm. <Second Layer Highly Sensitive Red Sensitive Emulsion Layer> 1000 g of the cyan coupler emulsion used in the first layer was mixed with 1 kg of red sensitive highly sensitive silver iodobromide emulsion (70 g silver gelatin).
(containing 60g of iodine and having an iodine content of 4.5 mol%) and coated to a dry film thickness of 2μ. <Third Layer Intermediate Layer> An emulsion obtained by dissolving 50 g of 2,5-di-t-octylhydroquinone in 100 c.c. of dibutyl phthalate and 100 c.c. of ethyl acetate, and stirring and emulsifying the solution with 1 kg of a 10% gelatin aqueous solution. 700g was mixed with 1kg of 10% gelatin and applied to a dry film thickness of 1.2μ. <4th layer low green sensitivity interemulsion layer> Magenta coupler 1-(2,4,6-trichlorophenyl)-3-{3-(2,4-di-t-amylphenoxyacetamide)benzamide }-5-
The emulsion for the first layer was prepared in the same manner except that 125 g of pyrazolone was used. 500 g of the obtained emulsifier was mixed with 1 kg of green-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, iodine content of 4.5 mol%), and dried. It was applied to a film thickness of 2.0μ. <5th layer Highly sensitive green-sensitive interemulsion layer> 1000g of magenta coupler emulsion used in the 4th layer
1 kg of green-sensitive highly iodine silver bromide emulsion (70 g of silver gelatin)
60 g, mixed with iodine content 2.5 mol%),
It was applied to a dry film thickness of 2μ. <6th layer middle layer> 700g of the emulsion used in the 3rd layer was mixed with 10% gelatin.
Kg and applied to a dry film thickness of 0.9μ. <7th layer yellow filter layer> Dry gelatin solution containing yellow colloidal silver
It was applied to a thickness of 1μ. <8th layer low-sensitivity blue-sensitivity emulsion layer> Yellow coupler α (pivaloyl)-α-(1-
benzyl-5-ethoxy-3-hydantoinyl)
-1 kg of blue-sensitive silver iodobromide emulsion (70 g of silver, 60 g of gelatin) (containing iodine content of 2.5 mol%) and coated to a dry film thickness of 2.0 μm. <9th layer Highly sensitive blue-sensitive emulsion layer> 1000 g of the same emulsion used in the 8th layer is mixed with 1 kg of blue-sensitive highly sensitive silver iodobromide emulsion (70 g of silver, 60 g of gelatin, iodine content is 2.5 mol%). Then, it was applied to a dry film thickness of 2.0 μm. <10th layer 2nd protective layer> 1 kg of emulsion used in the 3rd layer and 1 kg of 10% gelatin
It was mixed and applied to a dry film thickness of 1 μm. <11th layer 1st protective layer> A 10% gelatin aqueous solution containing a fine-grain silver iodobromide emulsion (grain size 0.15μ, iodine content 1 mol%) that has not been chemically sensitized is coated with a silver coating amount of 0.3 g/m ² , and a dry film is formed. Thickness 1μ
I applied it to make it look like this. Films B to C... Exemplary compounds (1) and (4) of the present invention in place of 2,5-di-t-octylhydroquinone
Films B~ were made in the same manner as Film A, except that emulsions containing these were used for the third, sixth, and tenth layers, respectively. The above films A to C were exposed to red light through a wedge whose gray density was continuously changed, and then subjected to the following reversal development process. Processing recipe Processing process Time Temperature First development 6′ 38℃ Water washing 2′ 〃 Inversion 2′ 38℃ Color development 6′ 〃 Adjustment 2′ 〃 Bleaching 6′ 〃 Fixing 4′ 〃 Water washing 4′ 〃 Stable 1′ Dry at room temperature The composition of the treatment solution used is as follows. First developer water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl 4-methyl 4-hydroxymethyl-
3 Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water to 1000ml (PH10.1) Reverse solution water 700ml Nitrilo-N-N-N-trimethylenephosphonic acid 6Na Salt 3g Stannous chloride (dihydrate) 1g p-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water to 1000ml Color developer water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium tertiary phosphate (12 hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 15g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfuric acid Salt 11g Ethylenediamine 3g Add water 1000ml Adjustment water 700ml Sodium sulfite 12g Ethylenediamine, sodium tetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water 1000ml Bleach solution water 800ml Ethylenediamine sodium tetraacetate (dihydrate) Salt) 2.0g Ethylenediaminetetraacetate ammonium (dihydrate) 120.0g Potassium bromide 100.0g Add water 1000ml Fixer water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1000ml Stabilized water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell 5.0ml Add water to 1000ml Measure the density of each developed film using a red filter and check the maximum color density (Dmax) and minimum density (Dmin). Ta. Furthermore, the maximum color density of the blue-sensitive layer and green-sensitive layer was examined using a blue filter and a green filter, respectively. The results are shown in the table below.

[Table] From the above table, it can be seen that when the compound of the present invention is used, the value of the minimum density of the red-sensitive layer becomes lower. This result shows that color staining is prevented by using the compound of the present invention. Example 4 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. cyan coupler DIR compound colored cyan coupler <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. magenta coupler colored magenta coupler DIR compound <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. yellow coupler <10th layer Highly sensitive blue-sensitive emulsion layer> 300 g of the emulsion (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 (1) of the present invention was used in place of -di-t-octylhydroquinone. These samples were exposed to red light through a wedge whose gray density was continuously changed, and the following treatments were carried out. 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 photographic light-sensitive material, which contains a compound represented by the following general formula () that does not form a dye upon reaction with an oxidized color developing agent as a color stain preventive agent. However, in the formula, R ¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a sulfonyl group, or a carbamoyl group. ^R2 , ^R3
each represents a substituted or unsubstituted aryl group or alkyl group, and may be the same or different.
One of A and B is -SO ₂ -, and the other is -CO-
It is. The ring substituted by OH may be a phenol ring, or may form a naphthol ring in collaboration with the atomic group Q.