JPS6134663B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material,
In particular, it relates to a silver halide photographic light-sensitive material in which a slightly water-soluble photographic yellow coupler is dispersed and contained in a hydrophilic organic colloid layer using a specific branched alkyl phosphoric acid. Conventionally, photographic additives that are sparingly soluble in water (e.g., oil-soluble couplers, antioxidants used to prevent color fogging or color mixing, antifading agents (e.g., alkylhydroquinones, alkylphenols, chromans, coumarons, etc.), hardeners, oil-soluble filter dyes, oil-soluble ultraviolet absorbers, DIR compounds (e.g., DIR hydroquinones, colorless DIR compounds,
etc.), developing agents, dye developers, DRR compounds, DDR couplers, etc.) are dissolved in suitable high-boiling organic solvents and dispersed in a solution of hydrophilic organic colloids, especially gelatin, in the presence of surfactants. It is used by being included in a hydrophilic organic colloid layer (for example, a photosensitive emulsion layer, a filter layer, a back layer, an antihalation layer, an intermediate layer, a protective layer, etc.). As high-boiling organic solvents, phthalate compounds and aryl phosphate compounds are particularly used. In particular, most of the solvents for photographic additives (for example, oil-soluble internal couplers) used in color and black-and-white photographic materials are of this type.
For example, US Patent No. 2322027, US Patent No. 2533514, US Patent No.
3287134, 3748141, 3779765, West German Patent No. 1152610, British Patent No. 1272561, West German Patent Application (OLS) No. 2629842, etc. Phthalate ester compounds and aryl phosphate ester compounds, which are high boiling point organic solvents, have an effect on coupler dispersibility, affinity with gelatin and colloid layers, stability of color images, and hue of color images. It has been widely used because of its chemical stability in photosensitive materials, availability at low cost, etc. However, such high boiling point organic solvents have problems with dispersibility of photographic additives that are poorly soluble in water, affinity with hydrophilic organic colloid layers, influence on photographic performance, chemical stability in photosensitive materials, etc. However, not all performances were completely satisfactory. For example, with these high-boiling point solvents, it is desirable to increase the weight ratio of the high-boiling point solvent to the yellow coupler to some extent in order to improve the stability of the dispersion and to improve the color development. There were drawbacks such as the color image storage stability of the resulting yellow image against light, heat, and humidity was significantly deteriorated. Such a phenomenon generally occurs with photographic oil-soluble yellow couplers, and impairs image storage stability after processing of color photographic materials, resulting in a decrease in color image density or discoloration (image formation However, this method was not always satisfactory, as it had drawbacks such as the balance of the three-color image being disrupted. On the other hand, it is known that when the weight ratio of yellow coupler to high-boiling solvent is lowered, color image storage stability is improved. However, in this case, the color density decreases, the stability of the emulsified dispersion deteriorates, the coupler precipitates, desirable photographic properties cannot be obtained due to aggregation, and in some cases, coating failure often occurs. . The incorporation of alkyl phosphate esters into color photographic materials has been proposed, for example, in Japanese Patent Publication No. 32,727/1983. However, this invention is clearly distinguished from the present invention because it uses an alkyl phosphate ester as a coupler solvent for a 5-pyrazolone azenta coupler. Furthermore, as described above, magenta images and yellow images have completely different resistances to light, heat, and humidity, and countermeasures to prevent fading require different techniques for each. Furthermore, in JP-A-53-13923, a yellow coupler,
A method of dispersing magenta coupler or cyan coupler with trinonyl phosphate or tridecyl phosphate is disclosed. However, this does not specify what effect can be obtained by dispersing a yellow coupler using a nonyl or decyl group with a branched carbon chain. The first object of the present invention is to provide a photographic material containing a yellow coupler as a dispersion using an alkyl phosphate ester having good dispersibility in a hydrophilic organic colloid. A second object of the present invention is to provide a photographic material manufactured using an alkyl phosphate ester that does not adversely affect photographic properties such as fog, sensitivity, and maximum image density. Thirdly, it is an object of the present invention to provide a color photographic material in which a yellow coupler is dispersed in an alkyl phosphate ester, and the yellow color image storage stability of photographic images is improved. These objectives are to disperse a photographic yellow coupler using an alkyl phosphate ester represented by the following general formula [] and to form an emulsified dispersion into at least one hydrophilic organic colloid layer of a silver halide photographic light-sensitive material. This was achieved by including General formula [] In the formula, R ₁ , R ₂ and R ₃ represent a branched alkyl group having 8 to 15 carbon atoms. R ₁ , R ₂ and R ₃ may be the same or different alkyl groups. Particularly preferred examples of R ₁ , R ₂ and R ₃ include branched alkyl groups having 9 to 10 carbon atoms. According to the present invention, by combining a branched alkyl phosphoric acid ester and an oil-soluble yellow coupler, the yellow color image storage stability can be significantly improved without reducing the color development and the stability of the emulsified dispersion. He succeeded in improving. Allyl esters of phosphoric acid, which have been used as good coupler solvents at first glance and are chemically similar compounds, do not have this effect, and the alkyl phosphoric esters that have been known so far do not have this effect. (e.g. trihexyl phosphate, dioctyl butyl phosphate, tri(n-octyl)-phosphate or tri(n-decyl)-phosphate, etc.) have given satisfactory results for this task. This is extremely unexpected considering that there is no such thing. I see, the application of alkyl phosphate esters to color photographic materials was published in Japanese Patent Publication No. 48-32727.
However, this is a combination with a 5-pyrazolone coupler, and for a 5-pyrazolone coupler and an azomethine dye derived therefrom,
Since the purpose is to provide a magenta color image with a desirable coloring hue by imparting a large dissolving power, unlike the objective effect of the present invention, it is not possible to exhibit an abnormal fading improvement effect on a yellow image as in the present invention. This was extremely unexpected. Furthermore, in JP-A No. 52-23933, it is combined with image intensification type processing, and the purpose is to reduce the intensification fog caused by the yellow two-equivalent coupler, which is not the objective effect of the present invention. They are very different. In conventionally used alkyl phosphate esters, solvents in which the total number of alkyl carbon atoms is 22 or less have a high dissolving power for yellow couplers, but have the effect of greatly impairing color image storage stability against light. On the other hand, among those with a large number of alkyl carbons (23 or more in total), some have low dissolving power for yellow couplers, resulting in poor stability of emulsified dispersions, and others have poor color-forming properties. It had characteristics such as being bad. However, it has been found that a very limited number of these long alkyl phosphate esters exhibit significantly good photographic properties. Alkyl phosphate esters with this effect have one alkyl carbon number of 8 to 15.
And it turns out that it is limited to those that are branched. These not only exhibited excellent coupler solubility and color development, but also exhibited an unexpected and remarkable effect of improving photofading properties, especially when used as a yellow coupler dispersion solvent. These will become clearer through the examples described later. Specific compound examples of branched alkyl phosphates preferably used in the present invention are shown below. Since the compound represented by the general formula [] passes through high temperatures during its synthesis process, the compound itself decomposes to produce a hydrolyzate. We have found that this hydrolyzate exacerbates the photobleaching of color images made from yellow couplers. In other words, if a compound represented by the general formula [] containing a hydrolyzate is used as a coupler solvent, the photobleaching property of the yellow image formed due to this oxide will deteriorate, and the compound represented by the general formula [] will be This inhibits the effect of improving the photobleaching property on the extremely excellent yellow image that it has. Therefore, in order to achieve the object of the present invention, among the compounds represented by the general formula (), it is more desirable to use those having an acid value of 5 or less, since they are more effective. The acid value is a guideline for the content of hydrolyzates among the impurities contained in the oil, and its measurement method is specified in the Japanese Industrial Standard JISK8004. The weight of solid potassium hydroxide required for neutralization by titration with potassium hydroxide is determined in mg, and this number is taken as the acid value. The larger the number of carbon atoms, the higher the need for high-temperature treatment to purify the compound, and for this reason, the acid value tends to increase as the number of carbon atoms increases. In order to achieve the object of the present invention, the compound represented by the general formula () preferably has an acid number of 1 or less, preferably 0.1 or less. The phosphoric acid esters of the present invention are JRvan Wazer
“Phosphorus and its Compounds” Vol 2,
It can be obtained by the reaction of phosphorus oxychloride and alcohol as described on page 1221.
At this time, a base is used to remove hydrogen chloride produced as a by-product during the reaction. This neutralization operation must be carried out extremely strictly, and by this operation, branched alkyl phosphates having a low acid value can be obtained. In addition, in order to obtain branched alkyl phosphates with low oxidation, it is necessary to wash thoroughly with water to remove salt after neutralization, and to reduce the water content in the crude product to 1% or less before distillation purification. It is. The specific method will be described below, but is not particularly limited. Synthesis example 1 Synthesis of tri(2-ethylhexyl) phosphate (compound example-1); 429.8g (3.3 mol) of 2-ethylhexyl alcohol, 237.3g (3.3 mol) of pyridine
mol) and 500 ml of chloroform,
Stir, cool, and add 153.4 g of phosphorus oxychloride to this.
(1 mol) was added dropwise to react. After completing the reaction by further heating under reflux for 2 hours, the mixture was thoroughly washed with water, a diluted aqueous solution of caustic soda, and water, and dried over anhydrous sodium sulfate. This solution was filtered, concentrated under reduced pressure, and then distilled to obtain 392.9 g (yield: 90.4%) of the target tri(2-ethylhexyl) phosphate. bp.183~
7℃/1mmHg Synthesis Example 2 Synthesis of tri(3,5,5-trimethylhexyl)phosphate (Compound Example-3); 3,5,5
- 476.1 g (3.3 moles) of trimethylhexanol, 237.3 g (3 moles) of pyridine and 600 g of chloroform
153.4 g (1 mol) of phosphorus oxychloride was added to the solution (15 minutes) while stirring and cooling, and after the dropwise addition, the mixture was heated and refluxed for 2 hours. This reaction solution was treated in the same manner as in Synthesis Example 1, and then distilled under reduced pressure.
411.9 g (yield: 86.4%) of tri(3,5,5-trimethylhexyl)phosphate was obtained as a fraction at 160° C./2×10 ⁻² to 3×10 ⁻² mmHg. Synthesis Example 3 Synthesis of tri(2-ethylhexyl) phosphate (compound-1) with a low acid value; 429.8 g (3.3 mol) of 2-ethylhexyl alcohol, pyridine
A solution consisting of 237.3 g (3 mol) and 500 ml of 700 form was stirred and cooled to -5°C, and 153.4 g (1 mol) of phosphorus oxychloride was added dropwise at below 10°C to react. After completing the reaction by further heating under reflux for 2 hours,
Double the amount of water was added to the system to thoroughly wash the oil layer. The pH of the aqueous layer was then adjusted with a 5% aqueous solution of sodium bicarbonate.
It was washed until the pH was within the range of 7.0±0.2, the oil layer was separated, anhydrous sodium sulfate was added, and it was left overnight to dry. This solution was filtered, concentrated under reduced pressure, and then immediately distilled, and the portion with a bp of 180 to 205°C/1.5 mmHg was collected and re-distilled. 369.4 g (yield: 85.0%) of target tri(2-ethylhexyl) phosphate was obtained. bp183
~7°/1 mmHg, and the acid value was measured according to JISK8004 and was 0.09. The amount of the branched alkyl phosphoric acid ester represented by the general formula () can be used in any ratio to the oil-soluble yellow coupler.
It is preferably used in a ratio of 0.05 to 10 (weight ratio), particularly preferably 0.1 to 2.0. The oil-soluble yellow coupler in the present invention is, for example, an acylacetoacide compound represented by the following general formula []. General formula [] In the formula, Y ₁ is an aliphatic group, aromatic group, or heterocyclic group, Y ₂ is an aromatic group or heterocyclic group, and X
is a hydrogen atom or a coupling-off group that can become an anion and leave by an oxidative coupling reaction with an aromatic primary amino developer. The aliphatic group represented by Y ₁ includes a substituted or unsubstituted alkyl group, and may be either chain or cyclic. Substituents for alkyl groups include alkenyl groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, amino groups, carboxy groups, acylamino groups, carbamoyl groups, imido groups, alkoxycarbonyl groups, acyloxy groups,
Examples include a sulfo group, a sulfonyl group, a sulfonamide group, a sulfamoyl group, and these groups themselves may further have substituents. Specific examples of aliphatic groups useful as Y ₁ include the following. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, 1-methylpentyl, 2-methylpentyl, neopentyl,
1,1-dimethylbutyl, hebutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 5-methylhexyl, 1,1-dimethylhexyl, octyl, 2-ethylhexyl, 1,1
-diethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 1,1-dimethylnonyldecyl, 1,1-diamylhexyl, 1-methyl-1-nonyldecyl, cyclopropyl, cyclobutyl, cyclopentyl , cyclohexyl, penzyl, phenethyl, allyl, oleyl, 7,7-
Dimethylnorbornyl, 1-methylcyclohexyl, 2-methoxyisopropyl, 2-penzylisopropyl, 2-phenoxyisopropyl, 2-
p-tert-butylphenoxyisopropyl, 2-
naphthoxyisopropyl, cinnamyl, α-aminoisopropyl, α-(N N-diethylamino)isopropyl, α-(succinimido)isopropyl, α-(phthalimido)isopropyl,
α-(acetylamino)isobutel, α-(benzenesulfonamido)isopropyl, etc. Furthermore, the aromatic groups represented by Y ₁ and Y ₂ include substituted or unsubstituted phenyl groups. Suitable substituents include halogen atom, nitro group, cyano group, thiocyano group, hydroxyl group, alkoxy group, aryloxy group, acyloxy group, alkyl group, alkenyl group, aryl group, amino group,
Carboxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylamino group, imide group, sulfo group, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfamoyl group, sulfonamido group In addition to monovalent substituents such as , ureido group, and thiourido group, divalent substituents that form a condensed ring with a phenyl group can be mentioned. Examples of the phenyl group having such a divalent substituent include a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, and a tetrahydronaphthyl group. Of course, these monovalent and divalent substituents may themselves have further substituents. Furthermore, the heterocyclic group represented by Y ₁ and Y ₂ is an alpha . It is bonded to the carbon atom of the carbonyl group of the acyl group in acylacetamide and the nitrogen atom of the amide group, respectively. Such heterocyclic groups include thiophene type, furan type, pyran type, chromene type, pyrrole type, pyrazole type, pyridine type, pyrazine type, pyrimidine type, pyritazine type,
Examples include indolizine series, thiazole series, imidazole series, oxazole series, and oxazine series. These heterocyclic groups are halogen atoms,
Nitro group, cyano group, thiocyano group, hydroxyl group, alkoxy group, aryloxy group, acyloxy group, alkyl group, alkenyl group, aryl group, amino group, carboxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group group, an acylamino group, an imide group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfamoyl group, a sulfonamido group, a ureido group, a thioureido group, and the like. Preferred leaving groups include JP-A-47-26133;
Unexamined Japanese Patent Publication 1973-73147, Unexamined Japanese Patent Publication No. 50-6341, Patent Application 1973-
113634, Japanese Patent Application No. 49-8124, Japanese Patent Application No. 49-37651, Special Publication No. 49-13576, Special Publication No. 48-29432, Japanese Patent Application No. 1973-
66835, phthalimide, succinimide, maleimide, hydantoin, glycolimide, oxazolidine-2,4-dione, thiazolidine-2,4-dione described in JP-A No. 48-94432 (publication); 49-122335, benzotriazole, benzimidazole, indazole, triazole, imidazole, pyrazole compounds described in JP-A No. 48-66834; saccharin compounds described in JP-A-48-25933; Urazol and parabanic acid compounds described in JP-A-48-66834; JP-A-49-
1229, cyclic monoimide compounds described in JP-A-50-28834 and JP-A-50-34232;
4-oxo-3,4-dihydro-1-H-2,1,3-benzothiadiazine- of specification No. 74004
Examples include S.S-dioxide compounds. It is desirable that the 2-equivalent yellow-forming couplers used in this invention be diffusion resistant. Diffusion resistance here refers to the fact that, during storage and processing, the coupler is substantially fixed in the hydrophilic colloid layer into which it is introduced, and does not migrate to other layers, as is commonly used with regard to color-forming couplers. This means that it will not leak into the processing solution. To impart diffusion resistance to the coupler, at least one hydrophobic group (e.g., alkyl group, alkylaryl group, etc.) having a total number of carbon atoms of about 8 or more is introduced into the molecule using a conventional method. It is carried out by. Many such hydrophobic groups are well known in the art, and all of them are used in the present invention. In the 2-equivalent yellow-forming coupler used in the present invention, Y ₁ , Y ₂ in the above formula ()
and such a hydrophobic group can be introduced into at least one of the leaving groups. In the above formula (), Y ₁ is a carbonyl group and 3
an alkyl group bonded through a carbon atom, especially a tert
2-equivalent yellow-forming couplers that are -butyl groups are preferred. Also preferred are 2-equivalent yellow-forming couplers in which Y ₁ is a phenyl group or a phenyl group substituted with a halogen atom, an amino group, an acylamino group, a sulfonamido group, a ureido group, an alkyl group, an alkoxy group or an aryloxy group. Furthermore,
In formula (), Y ₂ is a phenyl group or a halogen atom, a trifluoromethyl group, an amino group, an acylamino group, a sulfonamide group, a ureido group, an alkyl group, an alkoxy group, an aryloxy group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group A yellow-forming coupler which is a phenyl group substituted with a sulfo group, a sulfamoyl group or an imido group, particularly a compound represented by the following formula (), is preferred. General formula () In the formula, Q ₁ represents a halogen atom, an alkoxy group, an aryloxy group, a dialkylamino group, or an alkyl group, and Q ₂ represents the 4-position or 5-position of the anilide nucleus.
halogen atom, trifluoromethyl group, acylamino group, sulfonamide group, ureido group, alkyl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group,
Represents a carbamoyl group, sulfo group, sulfamoyl group or imido group. Y ₁ and X are each the same as those in formula (). Representative examples of compounds among the yellow-forming couplers used in the present invention are shown below. Generally well-known couplers other than yellow-forming couplers can be used to make color photographic materials using the present invention. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule. The coupler is 4 for silver ions.
Either equivalence or 2-equivalence may be used. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The coupler may be one in which the product of the coupling reaction is colorless. As the magenta color forming coupler, pyrazolone compounds, intazolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta coloring couplers that can be used include US Pat. No. 2,600,788 and US Pat.
No. 3062653, No. 3127269, No. 3311476,
3419391, 3519429, 3558319, 3519391, 3519429, 3558319,
No. 3582322, No. 3615506, No. 3834908, No.
3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665, OLS No. 2417945, OLS No. 2418959
No. 2424467, Special Publication No. 1973-6031, etc. As the cyan color-forming coupler, a phenol compound, a naphthol compound, etc. can be used. Specific examples are US Patent Nos. 2369929 and 2434272.
No. 2474293, No. 2521908, No. 2895826,
Same No. 3034892, No. 3311476, No. 3458315, Same No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, No. 4004929, West German Patent Application (OLS) No. 2414830, No. 2454329, JP-A-1977-
No. 59838, No. 51-26034, No. 48-5055, No. 51-
It is described in No. 146828. 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.
3790384, 3632345, West German patent application (OLS) 2414006, 2454301, 2454329
No., British Patent No. 953454, Japanese Unexamined Patent Publication No. 52-69624, same.
Those described in No. 49-122335 and Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat.
The one described in West German patent application (OLS) No. 2417914 can be used. Two or more of the above couplers can be contained in the same layer. The same compound may be contained in two or more different layers. In order to introduce couplers other than the yellow coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid 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), or boiling points from about 30°C to 150°C.
After dissolving in an organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl fropionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. Ru. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. These couplers are generally added in an amount of 2 x 10 ^-3 mol to 5 x 10 ^-1 mol, preferably 1 x 10 ^-2 mol to 5 x 10 ^-1 mol, per mol of silver in the emulsion layer. The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure, such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heterocyclic nucleus such as a thiobarbituric acid nucleus can be applied. Useful sensitizing dyes include, for example, German Patent No. 929080;
US Patent No. 2231658, US Patent No. 2493748, US Patent No. 2503776
No. 2519001, No. 2912329, No. 3656959,
No. 3672897, No. 3694217, British Patent No. 1242588
No. 44-14030. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are US Patent No. 2688545, US Patent No. 2977229, US Patent No.
No. 3397060, No. 3522052, No. 3527641, No. 3527641, No. 3522052, No. 3527641, No.
No. 3617293, No. 3628964, No. 3666480, No.
No. 3679428, No. 3703377, No. 3769301, No.
No. 3814609, No. 3837862, British Patent No. 1344281,
It is described in Special Publication No. 43-4936. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3635721
The combinations described in this issue are particularly useful. 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 (such as those described in US Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in US Pat. No. 3,314,794,
3352681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705,805)
No. 3,707,375), or benzoxazole compounds (for example, those described in U.S. Pat. No. 3,499,762);
) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These UV absorbers may be mordanted into certain layers. The photosensitive material of the present invention contains hydroquinone derivatives, aminophenol derivatives,
It may contain gallic acid derivatives, ascorbic acid derivatives, etc., and specific examples thereof are disclosed in U.S. Patent No. 2360290.
No. 2336327, No. 2403721, No. 2418, 613
No. 2675314, No. 2701197, No. 2704713,
No. 2728659, No. 2732300, No. 2735765, JP-A No. 50-92988, No. 50-92989, No. 50-93928
No. 50-110337, Special Publication No. 50-23813, etc. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization), etc. Various known surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides) , polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and non-ionic materials such as urethanes or ethers. surfactants; triterpenoid saponins, alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates,
Alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups: amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amine imides, Amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphoniums or sulfoniums containing aliphatic or heterocyclic rings. Cationic surfactants such as salts can be used. Specific examples of these surfactants are listed in the U.S. patent.
No. 2240472, No. 2831766, No. 3158484, No.
No. 3210191, No. 3294540, No. 3507660, British Patent No. 1012495, No. 1022878, No. 1179290, British Patent No.
No. 1198450, Japanese Unexamined Patent Publication No. 117414, US patent
No. 2739891, No. 2823123, No. 3068101, No.
No. 3415649, No. 3666478, No. 3756828, British Patent No. 1397218, US Patent No. 3133816, No. 3441413
No. 3475174, No. 3545974, No. 3726683,
No. 3843368, Belgian patent No. 731126, British patent
No. 1138514, No. 1159825, No. 1374780, Tokko Akira
40-378, 40-379, 43-13822, U.S. Patent No. 2271623, 2288226, 2944900, U.S. Pat.
No. 3253919, No. 3671247, No. 3772021, No.
3589906, 3666478, 3754924, West German patent application OLS 1961638, Japanese Patent Application Laid-open No. 50-59025, etc. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum,
chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1. 3,5-triacryloyl-hexahydro-S-triazine,
bis(vinylsulfonyl) methyl ether, etc.), active halogen compounds (2,4-dichloro-
6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc., alone. Or they can be used in combination. A specific example is US Patent No. 1870354
No. 2080019, No. 2726162, No. 2870013,
Same No. 2983611, No. 2992109, No. 3047394, Same No.
No. 3057723, No. 3103437, No. 3321313, No.
No. 3325287, No. 3362827, No. 3539644, No.
3543292, British Patent No. 676628, British Patent No. 825544, British Patent No.
1270578, German Patent No. 872153, German Patent No. 1090427,
It is described in Special Publication No. 34-7133, No. 46-1872, etc. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic light-sensitive materials. be done. Useful as flexible supports are films, baryta layers or alpha-olefin polymers of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally primed to improve adhesion with the photographic emulsion layer. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964) P. Grafkide, “Photographic Emulsion Chemistry” (Paul Montell, 1967); Press, 1966
It can be prepared using the method described in "Making and Coating Photographic Emulsions" by VL Zelikman et al. (Focal Press, 1964).
That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan.No.16,
Enzyme-treated gelatin as described on page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin derivatives include gelatin with acid halides,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are used. Specific examples include U.S. Patent Nos. 2614928, 3132945, 3186846, and U.S. Pat.
3312553, British Patent No. 861414, British Patent No. 1033189, British Patent No.
It is described in No. 1005784, Special Publication No. 42-26845, etc. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. In particular, polymers with some degree of compatibility with gelatin, such as acrylic acid,
Graft polymers with polymers such as methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate are preferred. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. Typical synthetic hydrophilic polymer substances include West German Patent Application (OLS) No. 2312708 and U.S. Patent No. 3620751.
No. 3879205 and Special Publication No. 7561 of 1973. Example 1 Yellow coupler α-pivalyl-α-5・5-di
-methyl-2・4-dioxo-3-oxazolidinyl-
2-chloro-5-[α-2′・4′-di-tert-
amylphenoxy) butylamido] acetanilide 27g,
A solution obtained by heating 27 g of the compound (-1) according to the present invention and 50 ml of ethyl acetate to 70°C was mixed with 50 g of gelatin and 2.0 g of sodium dodecylbenzenesulfonate.
The mixture was added to 300 ml of an aqueous solution containing g and stirred, then preheated and passed through a colloid mill five times. As a result, the coupler was finely emulsified and dispersed together with the solvent. The entire emulsified dispersion was added to 1.0 kg of photographic emulsion containing 54 g of silver iodobromide and 60 g of gelatin, and after adding 30 ml of a 5% acetone solution of triethylene phosphoramide as a hardening agent, the turbidity was removed. After adjusting the pH to 6.0, it was applied onto a triacetic acid fiber film base to a dry film thickness of 7.0 microns.
This is designated as sample A. Compounds (-3), (-5), (-6) according to the present invention were used instead of the above compound (-1) (-
A film was prepared using the same amount as in 1) and the same procedure. These are designated as samples B, C, and D. For comparison, in place of the above compound (-1), as a linear alkyl phosphate ester not included in this patent,
A film was prepared in the same manner as described above using the same amounts of tri-normal nonyl phosphate, tri-n-dodecyl phosphate, and commonly used dibutyl octyl phosphate, trigredyl phosphate and dibutyl phthalate. Samples E, F, and
Let them be G, H, and I. These films were subjected to stepwise sensitometric exposures and processed as follows. Color development process 1 Color development process 30℃ 4 minutes 2 Bleach fixing 30℃ 2 minutes 3 Washing with water 30℃ 2 minutes 4 Stabilization bath 30℃ 2 minutes Here, the composition of each processing solution in the color development process is as follows. be. Color developer Sodium metaborate 25 g Sodium sulfite 2 g Hydroxylamine (sulfate) 2 g Potassium bromide 0.5 g 6-Nitrobenzimidazole (borate) 0.02 g Sodium hydroxide 4 g Benzyl alcohol 15.8 ml Diethylene glycol 20 ml 4- (N-ethyl-N-β-metalsulfonamidoethyl)amino-2-methylaniline sesquisulfate 8 g Add water 1 (PH10.2) Bleach-fix solution Ferric salt of ethylenediaminetetraacetic acid 45 g Thiocyanic acid Ammonium 10% Sodium sulfite 10g Ammonium thiosulfate (60% by weight aqueous solution) 100ml Sodium ethylenediamine-tetraacetate 5g Add water 1 (PH6.9) Stable bath tartaric acid 10g Zinc sulfate 10g Sodium metaborate 20g Add water 1 Obtained A photostability test was conducted on the developed film. The sample was placed in a xenon tester at 2.0×10 ⁶
Exposure to lutu light for 10 days. The percentage decrease in color density of the samples exposed to light was then determined compared to samples that were not exposed to radiation. Table 1 shows the results of measuring the percentage decrease in density of color images with densities of 0.50 and 1.50.

[Table] As is clear from Table 1, it can be seen that the photofading of Samples A to D according to the present invention is significantly improved compared to Comparative Samples E to I. Furthermore, compared to Samples E and F using linear alkyl phosphate esters, the sample according to the present invention exhibits better color development. In Sample F, a change in the surface of the coated sample, which was thought to be due to coupler precipitation, occurred, and the gloss of the film surface was significantly reduced. Example 2 Compounds (-1), (-3), (
3 g of yellow coupler (-56) was added to 1 ml each of -5), (-6) and the comparison compounds tri-normal nonyl phosphate, tri-n-dodecyl phosphate, tricresyl phosphate, and dibutyl phthalate, and the mixture was heated to 100°C. The mixture was dissolved at 25°C, maintained at 25°C, and the time required for the compound to precipitate was investigated.

[Table] As shown in the above table, the compound (-1) according to the present invention,
(-3), (-5), and (-6) have excellent solution stability and do not cause defects on photographic images due to precipitation.
No major defects occur during application. Example 3 On a paper support laminated on both sides with polyethylene, the following first layer (bottom layer) to sixth layer (top layer)
A multilayer color photosensitive material (sample L) was prepared by coating (mg/m ² in the table represents the coating amount).

【table】

[Table] Compounds (-1), (-3), (-
5) was used as samples (Q) to (X). In samples (Q) to (X) as well, the ratio of the weight of the yellow coupler to the coupler solvent was 1:0.5, as in the comparative sample (P). Each sample was passed through a continuous wedge and subjected to 1/2 second exposure to blue light, green light, and red light, and was subjected to the following treatments. Process Time Temperature Color development 3'30'' 33℃ Bleach-fixing 1'30'' Water washing 2'00'' Drying Composition of color developer Benzyl alcohol 15 ml Sodium sulfite 5 g Potassium bromide 0.5 g Hydroxylamine sulfuric acid Salt 2.0g Sodium carbonate 30.0g Sodium nitrilotriacetate 2.0g 4-Amino-3-methyl-N-(β-methanesulfonamido)ethyl-aniline 5.0g Add water to 1000ml PH 10.1 Bleach-fix solution composition Ammonium thiosulfate Salt 105g Sodium sulfite 2g EDTA disodium salt 40g Sodium carbonate (H ₂ O) 5g Add water to 1000ml (PH7.0) Test the obtained sample using a xenon light fading tester (2.0x
A light fastness test was conducted at 10 ⁶ lux − 140 hr). The densities of yellow images with initial densities of 1.5 and 0.5 were measured after 140 hours, and the results of the percentage decrease in color density are shown in Table 3.

[Table] This result shows that when the branched alkyl phosphate ester according to the present invention is used in a fully multilayer system, good photographic properties are obtained and a yellow image that is particularly strong against light is formed. . Example 4 Regarding the compounds used as coupler solvents used in Samples A to F of Example 1, Japanese Industrial Standards
Acid value was measured according to JISK-8004. Next, compounds (-1), (-3), (-5) and (-
Samples JKLM and N were prepared in the same manner as in Example 1 using 6). Table 4 summarizes the acid values of the coupler solvents used in Samples A to F and J to M.

[Table] Each of the obtained samples was subjected to the same development treatment and photobleaching test as in Example 1. Table 5 shows the degree of light extinction in terms of density reduction rate (%).

[Table] From Table 5, it can be seen that the use of those of the general formula with a lower acid value further improves the photobleaching property. Preferred embodiments of the invention are as follows. 1 In the branched alkyl phosphate esters described in the claims, R ₁ , R ₂ of the general formula [],
In particular, R ₃ has 8 to 10 carbon atoms. 2. The yellow coupler described in the claims is represented by the general formula []. 3 In the claims, the weight ratio of the branched alkyl phosphate ester to the yellow coupler is
Must be 0.05 to 10 (weight ratio). 4 In the claims, the weight ratio of the branched alkyl phosphate ester to the yellow coupler is
Must be between 0.1 and 2.0 (weight ratio). 5. The yellow coupler in the claims is represented by the general formula []. 6. In the claims, the branched alkyl phosphate ester is tri-(3,5,5-trimethylhexyl) phosphate. 7. In the claims, the branched alkyl phosphate ester is tri-(3,6,6-trimethylheptyl)phosphate. 8 In the claims, the yellow coupler is α-
Pivaloyl-2-[2,4-dioxo-5.
5'-dimethyloxazolidin-3-ylco-2
-Chloro-5-[α-2,4-di-t-amylphenoxy)butanamide]acetanilide 9 In the claims, the coupler solution represented by the general formula () has an acid value of 5 or less. 10 In the claims, the coupler solvent represented by the general formula () has an acid value of 1 or less. 11 In the claims, the acid value of the coupler solvent represented by the general formula () is 0.1 or less.

Claims (1)

[Claims] 1. A silver halide photograph having at least one hydrophilic organic colloid layer containing a dispersed oil-soluble yellow coupler using a branched alkyl phosphoric acid ester represented by the following general formula [] photosensitive material. General formula [] R ₁ , R ₂ and R ₃ are branched alkyl groups having 8 to 15 carbon atoms, and each of R ₁ , R ₂ and R ₃ may be the same or different.