JPS6232780B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photographic material,
This is particularly true for color photographic materials that have a high dye formation yield and increase sensitivity in the color development process. By color-developing silver halide color photographic materials, the oxidized aromatic primary amine color developing agent and coupler react to produce indophenol, indoaniline, indamine, azomethine, etc.
It is known that phenoxazine, phenazine and similar dyes can be produced to form color images. In this system, a subtractive color method is usually used for color reproduction, using silver halide emulsions that are selectively sensitive to blue, green, and red, and color image forming agents of yellow, magenta, and cyan, which are complementary colors, respectively. is used. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or imidazolone coupler is used. Couplers are used, primarily phenolic couplers such as phenols and naphthols to form cyan images. Most couplers that form conventional color images are 4-equivalent couplers. That is, in order to form 1 mol of dye through a coupling reaction, development using 4 mol of silver halide as an oxidizing agent is theoretically required. In contrast, a 2-equivalent coupler with an active methylene group substituted with a group that oxidatively couples with the oxidation product of an aromatic primary amine developer produces 2 moles of halogenation to form 1 mole of dye. Only silver development is required.
With a 2-equivalent coupler, the amount of silver halide required to form a dye is only half that of a 4-equivalent coupler, so it is possible to speed up the processing of photosensitive materials by making the photosensitive layer thinner, and by reducing the film thickness. Many benefits are recognized in terms of improved photographic properties and economical efficiency. Several attempts have been proposed to make the 5-pyrazolone type coupler, which has been mainly used as a magenta-forming coupler, into two equivalents. For example, in U.S. Pat. No. 3,214,437 and U.S. Pat. No. 3,253,924, the 4-position of the pyrazolone is replaced by a thiocyano group, in U.S. Pat. No. 3,311,476 by an acyloxy group, and in U.S. Pat. Patent No. 3,617,291 describes substitution with a 2-triazolyl group, and US Pat. No. 3,522,052 describes substitution with a halogen atom. However, when these 4-substituted pyrazolone couplers are used, significant color fog may occur, the reaction activity may not be appropriate, or the couplers may be chemically unstable and may not develop color over time. This has been accompanied by some disadvantages, such as the fact that it changes into a substance, and furthermore, there are many difficulties in synthesizing it. It has also been previously known to substitute the 4-position of 5-pyrazolone with an alkylthio group, an arylthio group, or a heterocyclic thio group, as disclosed in US Pat. No. 3,227,554. However, many of these known thio-substituted pyrazolone compounds have inadequate reaction activity with the oxidation products of aromatic primary amine color developers, and furthermore, as a result of the coupling reaction, the resulting mercapto compounds exhibit strong photographic activity. Therefore, it is difficult to apply it to general color photosensitive materials, and the chemical stability of the coupler is also insufficient. Furthermore, the color development sensitivity of the above-mentioned two-equivalent magenta coupler is not necessarily sufficient to meet the recent technical problem of increasing the sensitivity of color photosensitive materials.
There has been a strong desire to develop a technique for increasing the sensitivity of the magenta image forming layer. Recently, it has been found that magenta couplers having an alkylthio leaving group have particularly high activity and high color development sensitivity (see Japanese Patent Application No. 136497-1972).
This is still insufficient to obtain a highly sensitive color light-sensitive material, and in order to further improve this, a technique of using this magenta coupler in combination with a 1-phenyl-3-pyrazolidone derivative has been considered, resulting in even higher sensitivity. It became possible to obtain sensitive photosensitive materials. This also improved the storage stability of 5-pyrazolone couplers having an alkylthio leaving group.
However, this combination technology has a side effect of increased fogging, and solving this problem is essential for putting the above combination technology into practical use. The purpose of the present invention is, firstly, to provide a color photosensitive material with high color development sensitivity of a magenta color image forming layer, a small amount of coated silver, and low fogging, and secondly, to provide a color photosensitive material that has a magenta color image forming layer that is free from alkylthio without increasing fogging. The purpose of this invention is to improve the storage stability of light-sensitive materials using magenta couplers, and the third purpose is to improve the light resistance and fastness of dyes produced from alkylthio separation magenta couplers. A combination of the coupler represented by the general formula () of the present application and a diffusible 1-phenyl-3-pyrazolidone derivative, and a diffusible 1-phenyl-3-pyrazolidone derivative.
- The above object cannot be achieved by a method in which the pyrazolidone derivative is dissolved in a low boiling point organic solvent such as methanol and added to the emulsion. The object of the present invention is to provide a 1-phenyl-3 having a diffusion-resistant group in an emulsion layer containing at least one coupler represented by the following general formula () and/or in a hydrophilic colloid layer adjacent to the emulsion layer. This is achieved by containing a pyrazolidone derivative and a hydroquinone derivative represented by the general formula () in the presence of a high-boiling organic solvent for photographic additives. The present invention includes mixing a coupler represented by the general formula () with a diffusion-resistant oil-soluble 1-phenyl-3-pyrazolidone derivative, dissolving the mixture in a high-boiling organic solvent for photographic additives, and dispersing the mixture in an emulsion layer. It is particularly preferable in that it has a large effect. Coupler represented by general formula (), present application 1-
It is more preferable to mix the phenyl-3-pyrazolidone derivative and the hydroquinone derivative represented by the general formula (), dissolve the mixture in a high-boiling organic solvent, and disperse the mixture in the emulsion layer because the effects of the present invention are even greater. General formula () In the formula, R ₁ represents an anilino group, an amylamino group, or a ureido group, R ₂ represents an aralkyl group, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group, and X ₁ , X ₂ , and X ₃ represent a hydrogen atom or an alkyl group. group, a halogen atom, an alkoxy group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, or a cyano group, X ₁ ,
X ₂ and X ₃ may be the same group or different groups. More specifically, R ₁ is an anilino group (e.g.
Phenylamino group, o-chlorophenylamino group, 2,4-dichlorophenylamino group, 2,4
-dichloro-5-methoxyphenylamino group, 2
-chloro-5-tetradecanamidephenylamino group, 2-chloro-5-{α-(2,4-di-t-
amylphenoxy)butyramide}phenylamino group, 2-chloro-5-{(3-octadecenyl)
succinimide}phenylamino group, 2-chloro-5-[α-{(3-t-butyl-4-hydroxy)phenoxy}tetradecanamide]phenylamino group, etc.), acylamino group (e.g., acetylamino group, butylamide group, α- (3-pentadecylphenoxy)butyramide group, n-tetradecanamide group, α-(2,4-di-t-amylphenoxy)butyramide group, 3-{α-(2.
4-di-t-amylphenoxy)butyramide}
benzamide group, benzamide group, 3-acetylamide benzamide group, etc.), ureido group (e.g. phenylureido group, methylureido group, 3-acetylamidobenzamide group, etc.),
{α-(2,4-di-tert-amylphenoxy)butyramide} phenylureido, etc.), and X ₁ , X ₂ , and X ₃ are hydrogen atoms, alkyl groups (e.g., methyl groups, ethyl groups, etc.), halogen atoms (chloro atom, bromine atom, fluorine atom), alkoxy group (methoxy group, ethoxy group, etc.), aryloxy group (e.g. phenyloxy group, naphthyloxy group, etc.), acylamino group (e.g. acetylamino group, α -(2,4-G-t-
(amylphenoxy)butylamide group, etc.), carbamoyl group (e.g., methylcarbamoyl, phenylcarbamoyl group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, phenylsulfamoyl group, etc.), sulfonyl group (e.g.,
(ethylsulfonyl, butylsulfonyl, methylsulfonyl, etc.), cyano group. R ₂ represents a straight chain or branched alkyl group having 1 to 22 carbon atoms,
May be replaced. Examples of substituted alkyl groups are
A methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, a tetradecyl group, an octadecyl group, or a heptadecyl group. Examples of branched alkyl groups are i-propyl and tert-butyl. Furthermore, R ₂ represents an aralkyl group (eg, benzyl group, 2-phenylethyl group) or an alkenyl group (eg, propenyl group). These alkyl groups, aralkyl groups and alkenyl groups each have a halogen atom, nitro, cyano, aryl,
alkoxy, aryloxy, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane, thiourethane, sulfonamide, heterocycle, arylsulfonyloxy, Alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio,
Alkylsulfinyl, arylsulfinyl,
alkylamino, dialkylamino, anilino,
N-arylanilino, N-alkylanilino,
It may be substituted with a substituent selected from N-acylanilino and hydroxy groups. Among those represented by the general formula (), couplers in which R ₂ is an alkyl group having 1 to 5 carbon atoms are particularly preferred in that the resulting dye has high fastness. Regarding the physical properties and manufacturing method of specific examples of the coupler represented by the general formula (), please refer to Japanese Patent Application No. 53-136497.
(Japanese Unexamined Patent Publication No. 55-62454). The general formula () of the present invention is as follows. General formula () R represents an alkyl group having 8 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Among the above alkyl groups and aryl groups, halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, acyloxy groups, carbamoyl groups, sulfo groups, Sulfamoyl group, sulfonamide group, N-
It may have a substituent such as an alkylamino group, an N-arylamino group, an acylamino group, an imide group, or a hydroxyl group. n represents a number from 1 to 4, and when n is 2 or more,
Each R may be the same or different. Specific examples of the compound represented by the general formula () are as follows. HQ-1 2,5-di-tert-octylhydroquinone HQ-2 2-tert-octyl-5-methylhydroquinone HQ-3 2,6-di-n-dodecyl-hydroquinone HQ-4 2-n-dodecylhydroquinone HQ -5 2,2'-methylenebis-5,5'-di-
tert-Butylhydroquinone HQ-6 2,5-di-n-octylhydroquinone HQ-7 2-dodecylcarbamoylhydroquinone HQ-8 2-(β-n-dodecyloxycarbonyl)ethylhydroquinone HQ-9 2-(N・N -dibutylcarbamoyl)hydroquinone HQ-10 2-n-dodecyl-5-chlorohydroquinone HQ-11 2-(2-octadecyl)-5-methylhydroquinone HQ-12 2,5-di-(p-methoxyphenyl)hydroquinone HQ-13 2-tert-octylhydroquinone HQ-14 2-[β-{3-(3-sulfobenzamide)benzamide}ethylhydroquinone HQ-15 2,5-dichloro-3,6-diphenylhydroquinone HQ-16 2・6-dimethyl-3-tert-octylhydroquinone HQ-17 2,3-dimethyl-5-tert-octylhydroquinone HQ-18 2-{β-(dodecanoyloxy)ethyl}carbamoylhydroquinone HQ-19 2-dodecyloxy Carbonylhydroquinone HQ-20 2-{β-(4-octanamidophenyl)ethyl}hydroquinone HQ-21 2-methyl-5-dodecylhydroquinone HQ-22 2,5-di-tert-hexylhydroquinone Used in the present invention These 1-phenyl-3-pyrazolidone derivatives can be used alone or in combination of two or more. The amount added is preferably 0.005 mol to 10 mol, preferably 0.01 mol to 2 mol, per mol of the 2-equivalent magenta coupler. The 1-phenyl-3-pyrazolidone derivatives of the present invention include those represented by the general formula (). General formula () In the formula, R ₃ represents an optionally substituted aryl group, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group,
Examples include aryloxy group, alkylthio group, arylthio group, acylamino group, nitro group, sulfonamino group, cyano group, hydroxyl group, sulfo group, carboxyl group, and alkyloxycarbonyl group, and particularly preferred ones include alkoxy group, aryloxy group, and alkylthio group. and arylthio groups.
R ₄ to _{R 7} each represent a hydrogen atom, an alkyl group, a substituted alkyl group, (substituents include an aryl group, a hydroxyl group,
halogen atom, acyloxy group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic group) aryl group, substituted aryl group (substituents include alkyl group, aryl group,
halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, amino group, alkylamino group, acylamino group, sulfonamino group, cyano group, nitro group, hydroxyl group), alkyloxy group, aryloxy group, or aralkyloxy represents a group. However, if each of R ₄ to _{R 7} has a carbon number of 6 or less, the aryl group of R ₃ has a substituent with a carbon number of 6 or more, and if R ₃ has a substituent with a carbon number of 6 or less, At least one of R ₄ to _{R 7} has 6 or more carbon atoms. The high boiling point organic solvent for photographic additives used in the present invention may be any known one, such as phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric esters (diphenyl phthalate, etc.) described in US Pat. No. 2,322,027, and phosphates, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., such as U.S. Pat.
No. 2835579, Special Publication No. 46-23233, U.S. Patent
No. 3287134, British Patent No. 958441, Japanese Unexamined Patent Publication No. 1973-
1031, UK Patent No. 1222753, US Patent No. 3936303,
JP-A-51-26037, JP-A-50-82078, US Pat. No. 2353262, US Pat. No. 285238, US Pat. No. 3554755,
No. 3676137, No. 3676142, No. 3700454, No.
No. 3748141, No. 3837863, OLS2538889, JP-A No. 51-27921, No. 51-27922, No. 51-26035
No. 51-26036, No. 50-62632, Japanese Unexamined Patent Publication No. 1973-
Also preferred are those described in US Pat. No. 29461, US Pat. No. 3,936,303, US Pat. To introduce a coupler or a 1-phenyl-3-pyrazolidone derivative into a hydrophilic colloid layer, the method described in US Pat. After being dissolved in an organic solvent, such as a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl fropionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, or methyl cellosolve acetate, 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. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be 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. A technique similar to the present invention is disclosed in Japanese Patent Application Laid-Open No. 130928/1983. However, this technology is not for 5-pyrazolone magenta couplers, but for pyrazole magenta couplers in which the 5th position of the ring is substituted with a sulfonyloxy group or a carbonyloxy group, rather than an oxo group, and it is clear from the data in the examples. In this coupler, the general formula of the present invention is ()
It is clearly distinguished from the present invention in that there is almost no effect of increasing color development sensitivity even when used in combination with the compound of
Moreover, it is truly unexpected that there is such a difference in effectiveness. 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). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. 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 having 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. 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 dye numbers. 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, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, as a nucleus having a ketomethylene structure. A 5- to 6-membered heteroartic ring 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,
Same No. 3672897, No. 3694217, No. 4025349, Same No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
No. 14030, No. 52-24844. 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. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. 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. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives,
It may also contain imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent No. 2400532,
No. 2423549, No. 2716062, No. 3617280, No.
No. 3772021, No. 3808003, British Patent No. 1488991,
Those described in, etc. can be used. 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-treated gelatin, acid-treated gelatin and oxygen-treated gelatin as described in Bull.Soc.Sci.Phot.Japan No. 16, p. 30 (1966) may also be used as the gelatin. or oxygen decomposition products can also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. A specific example is a US patent
No. 2614928, No. 3132945, No. 3186846, No. 3186846, No. 3132945, No. 3186846, No.
3312553, British Patent No. 861414, British Patent No. 1033189, British Patent No.
It is described in No. 1005784, JP-A-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, and styrene. can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. 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. 3,879,205, and Japanese Patent Application Laid-open No. 7561/1983. 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 red-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer,
It is usual that each blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photosensitive material prepared according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are listed in the British patent
No. 584609, No. 1177429, Unexamined Japanese Patent Publication No. 1977-85130, No.
No. 49-99620, No. 49-114420, No. 52-108115
No., U.S. Patent No. 2274782, U.S. Patent No. 2533472, U.S. Patent No.
No. 2956879, No. 3148187, No. 3177078, No.
No. 3247127, No. 3540887, No. 3575704, No.
No. 3653905, No. 3718472, No. 4071312, No. 3653905, No. 3718472, No. 4071312, No.
It is described in No. 4070352. In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat.
2701197, 2704713, 2728659, 2701197, 2704713, 2728659,
No. 2732300, No. 2735765, No. 2710, No. 801, No.
Hydroquinone derivatives described in No. 2816028, British Patent No. 1363921, etc., U.S. Patent No. 3457079,
Gallic acid derivatives described in US Pat. No. 3069262, etc., US Pat. No. 2735765, US Pat.
p-alkoxyphenols described in US Pat. No. 20977 and US Pat. No. 52-6623, US Pat.
No. 3573050, No. 3574627, No. 3764337, JP-A-Sho
Examples include p-oxyphenol derivatives described in No. 52-35633, No. 52-147434, and No. 52-152225, and bisphenols described in U.S. Pat. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include US Pat. No. 2,360,290 and US Pat. , No. 2403721, same
No. 2418613, No. 2675314, No. 2701197, No.
No. 2704713, No. 2728659, No. 2732300, No.
No. 2735765, Japanese Patent Publication No. 50-92988, No. 50-92989
No. 50-93928, No. 50-110337, No. 52-
It is described in No. 146235, Special Publication No. 50-23813, etc. The photosensitive material produced using 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 U.S. Pat. No. 3,533,794),
4-thiazolidone compounds (e.g. U.S. patent
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene compounds (e.g. U.S. patents)
4,045,229) or benzoxyzole compounds (eg, those described in US Pat. No. 3,700,455). Further, those described in US Pat. No. 3,499,762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may also be used. These UV absorbers may be mordanted into certain layers. In the photosensitive material produced using the present invention,
The photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. Specific examples of fluorescent whitening agents are U.S. Pat. No. 2,632,701, U.S. Pat.
It is described in British Patent No. 3359102, British Patent No. 852075, British Patent No. 1319763, etc. In the present invention, known couplers can be used in addition to the pyrazolone coupler represented by the general formula (). Preferred yellow couplers are benzoylacetanilide and pivaloylacetanilide compounds. A specific example of a yellow coupler that can be used is US Pat. No. 2,875,057. Same number 3265506. 3408194
No. 3551155, No. 3582322. No. 3725072,
Same number 3891445. West German patent number 1547868, West German application published
No. 2219917, No. 2261361, No. 2414006, British Patent No. 1425020, Japanese Patent Publication No. 10783, Japanese Patent Publication No. 1977-
No. 26133, No. 48-73147, No. 51-102636, No. 50
-6341, 50-123342, 50-130442, 50-123342, 50-130442,
No. 51-21827, No. 50-87650, No. 52-82424,
This is described in No. 52-115219, etc. As the magenta coloring coupler, pyrazolone compounds, indazolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta coloring couplers that can be used include U.S. 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, Japanese Patent Publication No. 1973
-20826, 52-58922, 49-129538, 52-58922, 49-129538,
No. 49-74024, No. 50-159336, No. 52-42121,
No. 49-74028, No. 50-60233, No. 51-26541
No. 53-55122, No. 53-55122, 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-
These are those described in No. 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.
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.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and JP-A-53-9116 can be used. Two or more of the above couplers can be contained in the same layer. The same compound may be included in two or more different layers. 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. Any known method can be used for photographic processing of the light-sensitive material produced using the present invention.
A known treatment liquid can be used. The processing temperature is usually chosen between 18℃ and 50℃, but 18
The temperature may be lower than °C or higher than 50 °C. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (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 Prese, 1966)
), pages 226-229, U.S. Patent No. 2193015,
Those described in No. 2592364, JP-A-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. Bleaching treatment may be performed simultaneously with fixing treatment, or may be performed separately. As bleaching agents, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. The photosensitive material made using the present invention is
No. 84636, JP-A-52-119934, JP-A-53-46732
No. 1986-9626, 1974-19741, 1973-37731, Japanese Patent Application No. 1976-76158, Japanese Patent Application No. 54-1976
It may be processed with a developing solution supplemented or maintained by the method described in Japanese Patent Application No. 76159 and Japanese Patent Application No. 54-102962. Bleach-fixing solutions used in photosensitive materials made using the present invention are disclosed in Japanese Patent Application Laid-open Nos. 46-781 and 48-49437;
No. 48-18191, No. 50-145231, No. 51-18541
No. 51-19535, No. 51-144620, Special Publication No. 51
It may also be recycled using the method described in No.-23178. Example 1 A coating composition having the following composition was coated on a transparent cellulose triacetate support, and a gelatin protective layer (1 g/m ² ) was coated on top of this layer to form samples A to G.
was created. Coating liquid composition Green-sensitive silver iodobromide emulsion (silver iodide 6 mol%, silver bromide
94 mol%, coated silver amount 1 g/m ² ) Magenta coupler coated amount 7×10 ⁻⁴ mol/m ² Additive compound according to the present invention (see Table 1) 7×
10 ^-5 mol/m ² Coupler dispersion catalyst...tricresyl phosphate

[Table] In addition to the above samples, a seed coating sample was prepared which was exactly the same as above except that no additives or compounds were included in the coating liquid composition. Sample these by matching them with the above sample.
A′ to G′. The same coated samples as Samples A to G were prepared, except that HQ-1 was used as the antifoggant and the amount added was 1/5 mol% of the magenta coupler.
A″～G″. Comparison coupler 1 Comparison coupler 2 Comparison coupler 3 These samples were exposed to light through an optical wedge and then subjected to the following treatments. Processing process Temperature (℃) Time 1 Color development 38℃ 3 minutes 15 seconds 2 Bleaching 〃 6 minutes 30 seconds 3 Washing with water 〃 2 minutes 4 Fixing 〃 4 minutes 5 Washing with water 〃 4 minutes 6 Stabilizing bath 〃 1 minute The treatment solution used had the following composition. Color developer 4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline monosulfate
5g Sodium sulfite 5g Hydroxylamine sulfate 2g Potassium carbonate 30g Potassium hydrogen carbonate 1.2g Potassium bromide 1.2g Sodium chloride 0.2g Trisodium nitrilotriacetate 1.2g Adjust the pH to 10.1 and add water to make a total volume of 1000ml Bleach solution Ethylenediamine tetraacetic acid iron () ammonium
100g Ethylenediaminetetraacetic acid disodium 10g Potassium bromide 150g Glacial acetic acid 10g Adjust the pH to 6.0 with ammonia water and add water to make the entire volume.
1 Fixer ammonium thiosulfate 150g Sodium sulfite 10g Sodium hydrogen sulfite 2.5g Adjust the pH to 6.0 and add water to total volume 1 Stable bath formalin (37%) Fuji Drywell 3ml Add water to total volume 1 Indicate the concentration of the processed sample in green Measurements were made using light, and the sensitivity was determined using the fog value and the ASA sensitivity display method. Next, the sensitivity ratio (this is referred to as S/S') of the sample containing only the additive (for example, A) to the sample containing neither the additive nor the hydroquinones (for example, A'), and the sample containing neither the additive nor the hydroquinones. The sensitivity ratio (this is referred to as S''/S') of a sample containing an additive and hydroquinones (for example, A'') was determined. This can be summarized as shown in Table 2.

[Table] As mentioned above, for the oxy-eliminating type and 4,5-disubstituted pyrazole type couplers, which have relatively low activity, the increase in fog due to the addition of phenidone is small, but at the same time, the increase in sensitivity is also small. On the other hand, in the highly active alkylthio splitting coupler according to the present invention, the increase in fog when phenidone is added is large, but the fog can be suppressed by adding an antifoggant and the increase in sensitivity can be maintained. Furthermore, magenta was obtained by exposing and developing samples A, A', A'', C, C', and C'' which were stored for 3 months under natural conditions (25℃, 60%RH) after coating. The maximum density of the color images was compared to the maximum density of these samples immediately after application. The results are as follows.

[Table] From the above table, it can be seen that the samples of the present invention have low fogging and excellent storage stability. Example 2 Same as Example 1 except that a silver iodobromide emulsion containing 3 mol% of iodine (containing 100 g of silver halide and 70 g of gelatin per 1 kg of emulsion) was used instead of the emulsion used in Example 1. A coated sample containing the coupler and additives was prepared and subjected to the reversal treatment as described below. As in Example 1, the increase in fog when a phenidone compound was added to the S-separation type 2-equivalent magenta coupler was significantly reduced. It was found that this effect was effectively prevented without causing any discomfort. Processing process Temperature (℃) Time (minutes) 1 First development 38℃ 3 2 Water Washing 〃 1 3 Reversal 〃 2 4 Color development 〃 4 5 Adjustment 〃 2 6 Bleaching 38℃ 6 7 Fixing 〃 4 8 Water Washing 4 9 Stability 1 10 Drying The treated solution has the following composition. First developer water 800ml Sodium tetrapolyphosphate 2.0g Sodium bisulfite 8.0g Sodium sulfite 37.0g 1-phenyl-3-pyrazolidone 0.38g Hydroquinone 5.5g Sodium carbonate (monohydrate) 28.0g Potassium bromide 1.5g Potassium iodide 13.0mg Sodium thiocyanate 1.4g Add water to total volume 1 Reverse liquid water 800ml Hexasodium nitrilo-N・N・N-trimethylenephosphonate 3.0g Stannous chloride (dihydrate) 1.0g Sodium hydroxide 8.0g Ice Acetic acid 15.0ml Add water to make total volume 1.0 Color developer water 800ml Sodium tetrapolyphosphate 2.0g Benzyl alcohol 5.0ml Sodium sulfite 7.5g Sodium triphosphate (12 hydrate) 36.0g Potassium bromide 1.0g Potassium iodide 90.0mg Sodium hydroxide 3.0g Citrazic acid 1.5g 4-Amino-3-methyl-N-ethyl-β-hydroxyethylaniline sesquisulfate monohydrate 11.0g Ethylenediamine 3.0g Add water to make a total volume 1.0 Adjustment water 800ml Glacial acetic acid 5.0 ml Sodium hydroxide 3.0g Dimethylaminoethaneisothiourea (dihydrochloride)
1.0g Add water to total volume 1 Bleach solution water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ethylenediaminetetraacetate iron () ammonium (dihydrate) 120.0g Potassium bromide 100.0g Add water to total volume 1 Fixing solution Water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water to total volume 1 Stable bath water 800ml Formalin (37%) 5.0ml Fuji Drywell 5.0ml Add water to total volume 1.0

Claims (1)

[Scope of Claims] 1. A 1-phenyl compound having a diffusion-resistant group in an emulsion layer containing at least one coupler represented by the following general formula () and/or in a hydrophilic colloid layer adjacent to the emulsion layer. A color photographic material comprising a 3-pyrazolidone derivative and a hydroquinone derivative represented by the general formula () in the presence of a high-boiling organic solvent for use as a photographic additive. General formula () In the formula, R ₁ represents an anilino group, an acylamino group, or a ureido group, R ₂ represents an aralkyl group, an alkyl group, or an alkenyl group, and X ₁ , X ₂ , and X ₃ represent a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group. , an aryloxy group, an acylamino group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, or a cyano group, and X ₁ , X ₂ and X ₃ may be the same group or different groups. General formula () In the formula, R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, an aryloxy group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group having 8 to 30 carbon atoms, and n represents a number from 1 to 4, and when n is 2 or more, each R may be the same or different.