JPH0419536B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) 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 trihydroxybenzene derivative as a color stain preventive agent. (Prior art) In a multilayer color photographic material containing a color forming coupler in a silver halide photographic emulsion and developed using a color developing agent such as paraphenylene diamine, the color developing agent generated during development is oxidized. It is well known that the phenomenon of so-called "color mixing" occurs in which pigments migrate into adjacent imaging layers to form undesirable pigments. Furthermore, it is known that during color development, an inconvenient "color fog" phenomenon occurs due to air oxidation of the color developer, fog of the emulsion, etc. (hereinafter, "color turbidity" and "color fog" are collectively referred to as (This will be referred to as ``color pollution''). Compounds added to auxiliary layers such as emulsion layers or interlayers to prevent color staining are listed in the US patent.
No. 2675314, No. 2701197, No. 2704713, No.
No. 2728659, No. 2732300, No. 2735765, No. 2735765, No. 2732300, No. 2735765, No.
Hydroquinone derivatives described in No. 2710801, No. 2816028, British Patent No. 1363921, etc.; US patent
Gallic acid derivatives described in No. 3457079, No. 3069262, Japanese Patent Publication No. 43-13496, etc.; US Patent No. 2735765
p-alkoxyphenols described in U.S. Patent No. 3,698,909, etc.; U.S. Pat.
p-oxyphenol derivatives as described in No. 3574627, No. 3764337, etc.; US Patent
No. 3432300, No. 3574620, No. 3698909, No.
Derivatives such as chroman and claman described in No. 3573050 and No. 4015990 are known. On the other hand, it is known that "color turbidity" phenomenon occurs in color diffusion transfer photographic materials as well as in ordinary color photographic materials, and in order to prevent this, hydroquinones (Japanese Patent Application Laid-Open No. 58-21249), Sulfonamide phenols (Research Disclosure 15162 (1973) p. 83, JP-A-55-72158, corresponding US Pat. No. 4,366,226) are used. 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 change in performance even after long-term storage, and also contributes to improving the light fastness of dye images formed by color development. is strongly desired. (Object of the Invention) 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. (Structure of the Invention) The above objects of the present invention have been achieved by incorporating a compound represented by the following general formula () into a silver halide color photographic light-sensitive material. General formula () In the formula, one of X <sub>1</sub> and X <sub>2</sub> represents a hydrogen atom and the other represents a hydroxyl group. R is a substituted or unsubstituted acyl group (preferably 10 to 40 carbon atoms; for example, a pentadecylcarbonyl group, a heptadecylcarbonyl group, a 2-
(dodecylcarbamoyl)benzenecarbonyl group, etc.), sulfonyl group (preferably 10 to 40 carbon atoms).
For example, dodecylsulfonyl group, 4-dodecylbenzenesulfonyl group, etc.), alkoxycarbonyl group (preferably 10 to 40 carbon atoms, e.g. dodecyloxycarbonyl group, 2-hexyldecyloxycarbonyl group, etc.), aryloxycarbonyl group (preferably Carbon number 10 to 40. For example, 2,4-di-(t)-
amylphenoxycarbonyl group), carbamoyl group (preferably 10 to 40 carbon atoms, e.g. N,N-didodecylcarbamoyl group, N-octadecylcarbamoyl group, etc.), sulfamoyl group (preferably 10 to 40 carbon atoms, e.g. N , N-dioctylsulfamoyl group, N-hexadecylsulfamoyl group, etc.), sulfoxide group (preferably 10 carbon atoms)
~30. For example, octadecyl sulfoxide group),
Acylamino group (preferably 10 to 40 carbon atoms, e.g. hexadecaneamide group), carbamoylamino group (preferably 10 to 40 carbon atoms, e.g. N, N
-dioctylcarbamoylamino group, etc.), alkoxycarbonylamino group (preferably 10 carbon atoms)
~40. For example, it represents a hexadecyloxycarbonylamino group) or an aryloxycarbonylamino group (preferably having 10 to 40 carbon atoms, such as a 3-pentadecylphenoxycarbonylamino group). However, the total number of carbon atoms in R is 10 or more. R can also include a polymer chain. In the general formula (), R is preferably an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group, and more preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group. is preferred. In the general formula (), of X <sub>1</sub> and X <sub>2</sub> , X <sub>1</sub> is OH
It is preferable that Specific examples of the compound of general formula () according to the present invention are shown below, but the present invention is not limited thereto. Synthesis examples of representative compounds are shown below. Other compounds can also be synthesized by following these synthesis examples. Synthesis of compound (11) (a) 4-(2-hexyldecanoyloxy)-1,2
-Synthesis of methylenedioxybenzene 13.8g of 3,4-methylenedioxyphenol and 9ml of pyridine were dissolved in 100ml of acetonitrile,
27.5 g of 2-hexyldecanoyl chloride prepared by a conventional method was added dropwise thereto over about 15 minutes. The system gradually heated up with the addition. After stirring for 2 hours,
The system was poured into diluted hydrochloric acid, extracted with ethyl acetate, concentrated, and purified by column chromatography to obtain 4-(2-hexyldecanoyloxy)- as a colorless oil.
31 g of 1,2-methylenedioxybenzene was obtained. (b) Synthesis of 2-(2-hexyldecanoyl)-4,5-methylenedioxyphenol 18.8 g of the product obtained in Synthesis Example 1 was dissolved in 200 ml of trichloroethane, and 7.2 g of anhydrous aluminum chloride was added thereto at room temperature. was added gradually. The system was then heated to reflux for 15 minutes and then cooled. The system was poured into dilute hydrochloric acid water, extracted with ethyl acetate, concentrated, and purified by column chromatography to obtain 2 as a pale yellow oil.
10 g of -(2-hexyldecanoyl)-4,5-methylenedioxyphenol was obtained. (c) Synthesis of Exemplified Compound (11) 7.5 g of the product of Preparation Example 2 was dissolved in 100 ml of dichloroethane, and 4 ml of boron tribromide was gradually added while stirring. After stirring at room temperature for 30 minutes, the system was poured into ice water.
Extracted and concentrated with ethyl acetate. Recrystallization from a mixed solvent of hexane and ethyl acetate gave 4.7 g of Exemplified Compound (11) as pale yellow crystals. Melting point 77-78℃. Calculated value as C <sub>22</sub> H <sub>36</sub> O <sub>4</sub> C; 72.49 H; 9.96 Actual value C; 72.43 H; 10.17 The compound of the present invention is usually used in the range of 1.0 × 10 <sup>-3</sup> to 1.0 × 10 <sup>-6</sup> mol/m <sup>2</sup> Ru. To explain in detail,
1.0 per layer when used as a color clouding prevention agent
×10 <sup>-3</sup> to 1.0 × 10 <sup>-5</sup> mol/m <sup>2</sup> , 1.0 × 10 <sup>-4</sup> to 1.0 × per layer when used as a color cast preventive agent
It is preferably used in a range of 10 <sup>−6</sup> mol/m <sup>2</sup> . In order to introduce the compound of the present invention into constituent layers such as emulsion layers and intermediate layers, 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),
Citrate esters (e.g. acetyl tributyl citrate), benzoate esters (e.g. octyl benzoate), alkylamides (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesates (e.g. tributyl trimesate), etc., or boiling point Approximately 30℃~
Organic solvents at 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After dissolving in methyl cellosolve acetate etc.,
Dispersed in hydrophilic colloids. 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. Silver halide color photography/
It is highly effective in preventing color staining of photosensitive 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 such as 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. 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.
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 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 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”, “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 form 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 carrying out this process, 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-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. 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, ferricyanides, dichromates, organic complexes of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilolyacetic acid, 1,3-diamino-
Aminopolycarboxylic acids such as 2-propanoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and 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 bromide and hydrocarbonic acid, and 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 Sample A Yellow coupler α-pivaloyl-α(2,4-dioxo-5,5′-dimethyloxazolidin-3-yl)- as 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 3.1 μ (coupler coverage 0.500×10 ^{− 3} mol/m ² ) Sample B Sample A was the same as Sample A except that the second layer contained 2,5-dioctylhydroquinone (hydroquinone coating amount 1.59×10 ^-4 mol/m ² ). B was produced. In addition, the following samples C to E were prepared. Sample Sample A except that the second layer contains 1.59×10 ^-4 mol/m ² of gallic acid octyl ester.
Sample C was prepared in the same manner as above. Sample D Sample D was prepared in the same manner as Sample A except that the second layer contained 1.59×10 ⁻⁴ mol/m ² of the exemplary compound (11) of the present invention. Sample E Sample A except that the second layer contains the exemplary compound (18) of the present invention and 1.59×10 ^-4 mol/m ²
Sample E was prepared in the same manner as above. Samples A to E prepared in this manner were successively exposed to light through wedges having different gray densities, and subjected to the following processing. 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] When it comes to mixed colors, the smaller the number, the less the color mixture. Therefore, it is clear that the compound of the present invention has an excellent ability to prevent color mixing (color turbidity) and exhibits a sufficient effect even when added in a small amount. Example 2 Preparation of Sample F 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 , coated silver amount 3.88×110 ^- 3 mol/m ² ,
The halogen composition of silver chlorobromide is 70 mol% silver bromide.
(30 mol% silver chloride) and a gelatin layer was applied thereon to a dry film thickness of 1 μm. Samples G to J Compounds of the present invention in addition to the above yellow couplers
Samples G to J were prepared in the same manner as sample F except that 0.02×10 ⁻³ mol/m ² of each of (1), (7), (11), and (15) were added. Each of the above samples was exposed to light 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. 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] Samples G to J using the compounds of the present invention have lower minimum densities than Sample F, indicating that color fog is improved. The above samples E to J (before exposure) were kept at a relative humidity of 50%,
After being stored at a temperature of 50°C for 3 days, the same exposure and processing as described above was performed, and a decrease in the maximum density and an increase in the minimum density were observed for sample F, whereas for samples G to J, a decrease in the maximum density and an increase in the minimum density were observed. Both the maximum and minimum concentration changes were very small. Example 3 Sample K 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> Cyan coupler 2-(heptafluorobutyluramide 1-5-{2'-(2″,4″-di-t-amylphenoxy)butyramide}phenol 100
Dissolve g in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate to make 1 kg of 10% gelatin aqueous solution.
500 g of the emulsion obtained by stirring and emulsifying was mixed with 1 kg of red-sensitive silver iodobromide emulsion (containing 70 g of silver, 60 g of gelatin, and iodine content of 4.5 mol%) to give a dry film thickness of 2 μm.
I applied it to make it look like this. <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> 2,5-di-t-octylhydroquinone 50g
dibutyl phthalate 100c.c. and ethyl acetate 100c.c.
700 g of the emulsion obtained by stirring and emulsifying with 1 kg of 10% gelatin aqueous solution was mixed with 1 kg of 10% gelatin and coated to a dry film thickness of 1.2 μm. <4th layer low green-sensitive emulsion layer> Magenta coupler 1-(2,4,6-trichlorophenyl)-3-{3-(2,4-di-t-amylphenoxyacetamide)benzamide} -5-
500 g of the emulsion obtained in the same manner as the emulsion of the first layer except that 125 g of pyrazolone was used was mixed with 1 kg of green-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, the iodine content was 2.5 mol%), It was applied to a dry film thickness of 2.0μ. <5th layer Highly green sensitive emulsion 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 of iodine (2.5 mol %) was mixed and coated to a dry film thickness of 2 μm. <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-sensitive emulsion layer> Yellow coupler d (pivaloyl)-d-(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. Samples L and M...Samples except that emulsions containing exemplary compounds (19) and (23) of the present invention were used in the third, sixth, and tenth layers, respectively, instead of di-t-octylhydroquinone. Samples L and M, which are the same as K, were made. The above-mentioned films K to M 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 1st development 6' 38℃ Washing with water 2' Inversion 2' Color developer 6' Adjustment 2' Bleaching 6' Fixing 4' Washing with water 4′ 〃 Stable 1′ Drying at room temperature The following composition of the processing solution is used. First developer water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl 4-methyl 4-hydroxylmethyl-3-pyrazolidone 2g Potassium bromide 2.5g Thiocyanine Potassium acid 1.2g Potassium iodide (0.1% solution) 2ml Add water to 1000ml (PH10.1) Inversion liquid water 700ml Nitrilo-N-N-N-trimethylenephosphonic acid 6Na salt 3g Stannous chloride (diwater) Salt) 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 triphosphate (12 hydrate) 36g Potassium bromide 1g Iodine Potassium chloride (0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 15g N.ethyl-N-(β-methanesulfonamidoethyl)-3.methyl-4-aminoaniline sulfate 11g Ethylenediamine 3g Add water to 1000ml Adjustment liquid water 00ml Sodium sulfite
12g Ethylenediamine, sodium tetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water to 1000ml Bleach solution water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Iron()ammonium ethylenediaminetetraacetate (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 Stable solution water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell 5.0 ml of water was added and each film was developed to 1000 ml. The density of each film was measured using a red filter, and the maximum color density (Dmax) and minimum density (Dmin) were determined. 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 thiacetate 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 <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 of which was mixed with 1 kg of a high-sensitivity red-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. <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. 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 sample thus prepared is referred to as N. In the above, as the emulsion of the fourth layer, 2,5
Sample O was prepared in the same manner except that the compound (11) 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 Pre-bath 30 seconds 3 Bleaching 4 minutes 20 seconds 4 Fixing 4 minutes 20 seconds 5 Washing 3 minutes 15 seconds 6 Stability 30 seconds The composition of the processing solution 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 to 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 Add water to 1.0 PH6.6 Stabilizing liquid formalin (40%) 8.0ml Add water to 1.0 The developed samples N and O were measured for concentration using a green filter, and the maximum color density and minimum color density were determined. When the color density (green sensitive layer) was examined, it was found that the magenta color density of sample O using the compound of the present invention was lower than that of sample N, indicating that color mixing (color turbidity) was better prevented.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic material characterized by containing a compound represented by the following general formula (). () (In the formula, one of X ¹ and X ² represents a hydrogen atom and the other represents a hydroxyl group. R is a substituted or unsubstituted acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, Represents a sulfoxide group, acylamino group, carbamoylamino group, alkoxycarbonylamino group, or aryloxycarbonylamino group.However, the total number of carbon atoms in R is 10 or more.)