JPS5942302B2 - Karasya Shinzairiyou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic material in which the storage stability of magenta dye images is improved, and in particular, a specific magenta dye and a bisphenol derivative are added to improve the storage stability of the obtained magenta dye images. This invention relates to a color photographic material characterized by containing:

It is well known that in a silver halide color photographic light-sensitive material, a color image is obtained by forming a dye image by a color development process using an oxidative condensation reaction between an aromatic primary amino compound and a coupler.

It is desired that the dye image produced in this manner is robust against light, heat, moisture, etc., and does not change color or fade. However, the fastness to ultraviolet rays or visible light (hereinafter referred to as light resistance) is still not satisfactory, and it is well known that the color fades relatively easily when exposed to ultraviolet rays or visible light. ing. In order to eliminate these drawbacks, various proposals have been made, including the use of various couplers with low fading properties and the addition of anti-fading agents to improve light resistance. Conventionally, compounds such as pyrazolone, cyanoacetyl and intazolone are known as magenta dye-forming couplers. For example, various methods have been proposed for adding and blending ultraviolet absorbers to color photographic materials to improve the light resistance of dye images.
However, in order to provide satisfactory lightfastness to a dye image using a UV absorber, a relatively large amount of UV absorber is required, and in this case, the dye image is significantly contaminated due to the coloring of the UV absorber itself. There were many things that happened. Furthermore, even when an ultraviolet absorber is used, it has no effect on preventing dye images from fading due to visible light, and there are limits to the improvement of light resistance by ultraviolet absorbers. In addition, special public service in 1977-
No. 8338, Special Publication No. 1973-6208, Special Publication No. 1977-1
4034 and US Pat. No. 3,432,300, etc., 5-hydroxycoumaran, 5-chromanol,
It has been proposed to use 6-chromanol, dihydroxyspirochromans, and the like. However, although these compounds do show an effect on the light resistance of dyes, their effect is not sufficient, and furthermore, the areas where unreacted couplers remain, that is, the unexposed areas, may turn so-called yellow (
There was a problem that Y-stain (hereinafter referred to as Y-stain) was generated, and it was not sufficient to compensate for the drawbacks of the conventional method. Especially 320-3
Light with a wavelength of 70 nm was undesirable because Y-stain was likely to occur. When Y-stain occurs in unexposed areas, the commercial value of the finished color print photographic material is significantly reduced. As described above, conventional magenta dye images do not have sufficient light fastness, and even when an anti-fading agent is used, Y-stains occur in unexposed areas.

In view of these circumstances, the inventors of the present invention have conducted extensive research and found that the compound represented by the following general formula coexists with a dye image formed from a 3-anilino-5-pyrazolone type coupler (however, the compound represented by the following general formula It has been found that a magenta dye image with extremely excellent light fastness can be obtained without generating Y-stain by excluding the case where the compound represented by (4) is further contained. (In the formula, Rl, R2, R3 and R4 have 1 to 1 carbon atom
18 alkyl groups, the total number of carbon atoms of Rl, R2, R3 and R4 is 32 or less, X is a simple bond,
An oxygen atom, a sulfur atom, a sulfonyl group or +CH+n, R5 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 3.

), where R2, R3 and R4 are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkoxy group, an alkenyl group, an alkenoxy group, an acylamino group, a halogen atom, an alkylthio group, an arylthio group , diacylamino group, acyl group, sulfonamido group, alkylamino group, alkoxycarbonyl group, and acyloxy group, and these may be the same or different.

A represents a nonmetallic atom necessary to complete/form a 5-negative or 6-membered ring together with \c=c'-0-.

) The compounds represented by the above general formula according to the present invention are disclosed in U.S. Pat. No. 2,792,428, U.S. Pat.
Specification No. 41619, Japanese Patent Publication No. 40-16539, Japanese Patent Publication No. 50-6338 Journal of the Chemical Society, p. 243, 1954 (Jour
It can be synthesized according to the method described in naIOfchemicalSociety).

Typical specific examples of the compound represented by the above general formula are shown below.

The compound represented by the above general formula according to the present invention is preferably added to the magenta layer, but may be added to other layers, especially layers adjacent to the magenta layer.

The compound represented by the above general formula according to the present invention is oil-soluble, and the general formula includes US Pat. No. 2,322,027 and US Pat.
No. 01170, No. 2801171, No. 22721
According to the method described in No. 91 and No. 2304940, the 3-anilino-5-pyrazolone type coupler is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, and then dispersed and halogenated. It is preferable to add it to a silver emulsion, and at this time, there is no problem in using a hydroquinone derivative, an ultraviolet absorber, etc. in combination, if necessary. At this time, there is no problem in using a mixture of two or more kinds of compounds represented by the general formula according to the present invention. Furthermore, to explain in detail the method of adding the compounds according to the present invention, one or more of the compounds, a 3-anilino-5-pyrazolone type coupler, and if necessary, a hydroquinone derivative, an ultraviolet absorber, etc. are added simultaneously to an organic compound. Acid amides, carpamates, esters, ketones, urea derivatives, etc., especially di-n-butyl phthalate, tritalesyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate , N,N-ginithyl-caprylamidobutyl, n-pentadecyl phenyl ether or fluorine paraffin, and if necessary, add ethyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexanetetrahydrofuran, etc. Dissolved in a low boiling point solvent (these high boiling point solvents and low boiling point solvents may be used alone or in combination) anionic surfactants such as alkylbenzene sulfohepta acids and alkylnaphthalene sulfonic acids and/or It is mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing a nonionic surfactant such as zorbitan sesquioleate and zorbitan monolaurate, and emulsified and dispersed using a high-speed rotating mixer, colloid mill, or ultrasonic dispersion device. , can be added to silver halide emulsions for use. If the 3-anilino-5-pyrazolone type coupler used at this time is diffusive, it should be added to the color developing solution to emulsify and disperse only the compound represented by the above general formula according to the present invention. However, it may be used by adding it to a silver halide emulsion.

Further, the compound represented by the above general formula according to the present invention has a sufficient effect even if it is incorporated into the color photographic material obtained after developing the silver halide color photographic light-sensitive material.

The amount of the compound represented by the above general formula according to the present invention to be added is not particularly limited, since the compound is substantially colorless and does not cause any adverse effects such as coloring contamination by itself. It is sufficient if the amount is about 159 per mole, and mainly for economic reasons, in silver halide color photographic light-sensitive materials containing couplers, the amount is 5 to 300 by weight relative to the commonly used 3-anilino-5-pyrazolone type coupler. % is preferred, especially 10-1
00% by weight is preferred, and in silver halide color photographic light-sensitive materials containing no coupler, 10 to 10,011, particularly 15 to 609, per mole of silver halide is preferred.

The 3-anilino-5-pyrazolone type magenta coupler used in the present invention typically includes a compound represented by the following general formula (1).

In the formula, X is a methyl group, an ethyl group, a tert-butyl group,
Alkyl groups such as octyl group and dodecyl group, phenyl group,
Aryl groups such as tolyl group, alkoxy groups such as methoxy group, ethoxy group, octyloxy group, phenoxy group, p-
Tert-butylphenoxy group, aryloxy group such as naphthoxy group, N-substituted amino group such as methylamino group, diethylamino group, anilino group, amide group such as acetamido group, butylamide group, methylsulfonamide group, diacylamido group, etc. Y represents a halogen atom such as Y
is phenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,4,6-trichlorophenyl group, 2
-promophenyl group, 3,5-dipromophenyl group, 2
-cyanophenyl group, 4-cyanophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 4-butylphenyl group, 2-tri- Fluoromethylphenyl group, 2-ethoxyphenyl group, 2-phenylphenyl group, 4-phenylphenyl group, 4-phenoxyphenyl group, 2-chloro-5-cyanophenyl group, 5-chloro-2-methylphenyl group, 2 , 6-dichloro-4-methylphenyl group, 2-chloro-4,6-dimethylphenyl group, 2,6-dichloro-4-methoxyphenyl group, 2,6-dichloro-4-nitrophenyl group, 2
, 4,6-trimethyl-3-nitrophenyl group, 2,4
, 6-trimethyl-3-acetamidophenyl group, or 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, 2-oxazolyl group, 2-imidazolyl group, 2-benzimidazolyl group, etc. represents a heterocyclic group having 5- and 6-membered rings, W represents a hydrophobic ballast group, and V represents a hydrogen atom or a group as defined for X or W. Furthermore, Z is hydrogen/
A1 atom or a group represented by -N or \. /
"1 represents a coupling-off group other than the group represented by N\A-, and A1 and A2 may be the same or different,
hydrogen atom, methyl group, ethyl group, propyl group, respectively.
Substituted or unsubstituted alkyl groups such as hydroxyethyl group, methoxycarbonylethyl group, acetoxyethyl group, ethoxyethyl group, penzyl group, allyl group, substituted or unsubstituted phenyl group, aryl group such as naphthyl group,
Although it represents a heterocyclic group such as a pyridyl group, A1 and A2 are not hydrogen atoms at the same time, and A and A2 may bond to each other to form a 5- or 6-membered ring containing a nitrogen atom. , the ring includes an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, a cyano group, a nitro group, an acylamino group, an acyl group, a carbamoyl group,
It may have a substituent such as a sulfamoyl group, a carboxy group, a sulfone group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonamide group, a multi-ring group, a halogen atom, and the 5- or 6-membered ring may have a saturated Alternatively, it may have an unsaturated fused ring, and the saturated or unsaturated fused ring represents a group which may have the same substituent as the 5- or 6-membered ring.

However, if A and A2 are bonded to each other and have two or more nitrogen atoms in a five- or six-membered ring containing a nitrogen atom, then
The membered or 6-membered ring does not have a fused aromatic ring, and examples of preferred 5- or 6-membered rings include pyrrolidine, piperidine, pyrrole, morpholine, tetrahydroisoquinoline, piperazine, hydantoin, saccharin, oxazoline, imidazoline, Examples include imidazolidine, indoline, thiazoline, thiazolidine, triazine and phthalimide. The term coupling-off group herein has the meaning commonly used with respect to dye-forming couplers, such that the coupler can be separated from the active carbon atom at the coupling position by coupling with the oxidation product of an aromatic primary amino color developing agent. represents a group. The term hydrophobic ballast group also has the meaning commonly used with respect to dye-forming couplers, and refers to hydrophobic ballast groups that are incorporated into the coupler molecule to substantially immobilize the coupler in a designated hydrophilic colloid layer and render it resistant to diffusion. Represents a sexual group.
The coupling-off group in the magenta dye-forming coupler used in the present invention includes U.S. Pat.
No. 0, No. 2688539, No. 2725292,
A group bonded to the coupling position of a so-called force coupler described in British Patent No. 2983608, British Patent No. 3005712, British Patent No. 800262, British Patent No. 1044778, etc.
U.S. Patent No. 3148062, U.S. Patent No. 3227554,
Nos. 3,617,291, U.S. Pat.
Examples include groups bonded to the coupling position of couplers described in Japanese Patent No. 37, Japanese Patent No. 3311476, and Japanese Patent No. 3419391.

Typical examples include thiocyano group, acetoxy group, dodecanoyloxy group, octadecanoyloxy group, 3-pentadecylphenoxyacetoxy group, benzoyloxy group, β-naphtholoxy group, 3-[γ-(2 , 4-di-Tert-amylphenoxy)butyramide] acyloxy group such as benzoyloxy group, phenoxy group, p
- Aryloxy groups such as chlorophenoxy group, p-nitrophenoxy group, naphthoxy group, aralkyloxycarbonyloxy group such as benzyloxycarbonyloxy group, alkyloxycarbonyloxy group such as ethyloxycarbonyloxy group, chlorine, bromine, halogen atom such as element, phenylazo group, hydroxyphenylazo group, chlorophenylazo group, methylphenylazo group,
Aryl azo groups such as methoxyphenylazo group and naphthylazo group; 2-aryl triazolyl groups such as 2-benzotriazolyl group and 2-naphthotriazolyl group; arylthio groups such as phenylthio group; Examples include heterothio groups such as ruthio group, 2-benzoxazolylthio group and 2-benzimidazolylthio group, cycloalkylthio group such as cyclohexylthio group, and cycloalkoxy group.

The hydrophobic ballast group in the magenta dye-forming coupler used in the present invention is generally a group containing 8 or more carbon atoms.

An upper limit of about 32 carbon atoms is useful for normal purposes. Suitable hydrophobic ballast groups are described, for example, in U.S. Pat.
No. 7344, Specification No. 3418129, Special Publication No. 1973
As described in Japanese Patent No. 27563 and Japanese Patent No. 45-19035, a large number of them are known, and these can be advantageously applied in the present invention. Typical hydrophobic groups include alkyl groups, alkenyl groups, alkoxyalkyl groups, alkyl-substituted aryl groups, alkoxy-substituted aryl groups, 4-phenyl groups, etc., and these groups include, for example, halogen atoms such as fluorine and chlorine. , a nitro group, a cyano group, an alkoxycarbonyl group, an amide group, a carbamoyl group, a sulfonamide group, or the like.
Specific examples of these groups include the following.

The hydrophobic ballast group is -0- -S- -N) as the linking moiety of the anilino group to the aromatic nucleus.
＼) etc. may be included.

Bispyrazolones in which two molecules of pyrazolone are bonded via V, W, Y or Z in the general formula (1) are also included in the 3-anilino-5-pyrazolone type magenta coupler used in the present invention.

Among the compounds represented by the general formula (1), Y is a halogen atom, an alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group at least one of the ortho positions,
A phenyl group having a nitro group, an aryloxy group, an acylamino group, or a cyano group is excellent in that the coupler itself has high stability against heat. Among the magenta dye image-forming couplers used in the present invention, compounds represented by the following general formula () are particularly useful.

In the formula, W and Z have the same meanings as in general formula (1), and X is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, a cyano group. or represents a nitro group, Yl, Y2 and Y3 represent a halogen atom, an alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a nitro group, an anyloxy type, a cyano group or an acylamino group;
2 and Y3 may be the same or different.

The number of carbon atoms contained in the group represented by Yl, Y2 or Y3 in the general formula () is preferably up to about 6 each.

In particular, in the general formula (), the substituted phenyl group at position 11 of pyrazolone is 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,
4,6-trichlorophenyl group, 2,5-dipromphenyl group, 2,4-dipromphenyl 2,5-dipromphenyl group, 2,4-dipromphenyl group, 2,6-dipromphenyl group, 2,4,6-tripromphenyl group enyl group,
2,4-dichloro-6-methylphenyl group, 2,6-dichloro-4-methylphenyl group, 2,4-dichloro-6
-methoxyphenyl group, 2,6-dichloro-4-methoxyphenyl group, 2-chloro-4-nitrophenyl group, 2
-Chloro-5-nitrophenyl groups, etc., have characteristics that are particularly desirable for magenta color images in terms of color reproduction (absorption polarity is 530 to 565 microns It is particularly excellent because it has low absorption in the blue and red light regions.

Specific examples of the 3-anilino-5-pyrazolone type magenta dye image-forming coupler used in the present invention are shown below.

Exemplary Couplers These 3-anilino-5-pyrazolone type magenta couplers are described in, for example, Mokukoku Patent No. 3684514, British Patent No. 1183515, Japanese Patent Publication No. 6031-1970, Japanese Patent Publication No. 6035-1973, Japanese Patent Publication No. 15754-1987. Publications, Special Publication No. 55-10063, Special Publication No. 54-37494
No., JP-A-49-117034, JP-A-49-123
No. 033, U.S. Pat. No. 3,419,391, U.S. Pat. No. 3,615
No. 506, No. 3677764, British Patent No. 9562
No. 61, No. 1249287, German Published Patent No. 213
Specification No. 3655, Japanese Patent Publication No. 45-40757, No. 46
-19032 Publication, Japanese Patent Publication No. 55-31460, Japanese Patent Publication No. 55-29420, Japanese Patent Publication No. 49-92066, Japanese Patent Publication No. 53-33846, Japanese Patent Publication No. 50-13041, etc. Therefore, it can be synthesized.

These 3-anilino-5-pyrazocan type couplers used in the silver halide color photographic light-sensitive material according to the present invention generally have a concentration of 5 to 50% relative to silver halide when present in the silver halide color photographic light-sensitive material. It is used in mole %, preferably 10 to 30 mole %, and when present in the developer, generally about 0.5 to 3.0 mole %.
9/11 is preferably used at about 1.0 to 2.0 θ/l. In this case, the 3-anilino-5-pyrazolone type couplers may be used alone or in combination of two or more types, and when two or more types are used in combination, the amount used is the amount mentioned above. Furthermore, silver halide emulsions contain hydroquinone derivatives, which are antioxidants that have been known for a long time, such as U.S. Pat. No. 3,236,893, U.S. Pat.
No. 32300, No. 2728659, No. 27225
No. 56, No. 2710801, No. 2704713, No. 2701197, No. 2675314, No. 2418613, No. 2403721, No. 238
No. 4658, No. 2360290, No. 233632
No. 7, British Patent No. 557750, British Patent No. 557802, German Published Patent No. 2149789, Japanese Patent Publication No. 4
4-54116, JP-A-46-2128, Journal of the Organ Chemistry Vol. 72, pp. 772-774 (JournalOf[HeOrga
Chemical compounds such as nicChemisLry) may be used in combination.

Also, among these hydroquinone derivatives, those in which the substituent on the aromatic nucleus is a substituted or unsubstituted alkyl group are particularly effective as 3-anilino-5-pyrazolone type couplers used in the present invention, and these are particularly preferred compounds. as 2,5-dioctylhydroquinone, 2,5
-di-Tert-acyl-hydroquinone and 2,5
-di-Tert-butyl-hydrokyl. The silver halide emulsion used in the silver halide color photographic light-sensitive material according to the present invention generally has silver halide grains dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide, silver iodide, etc. Silver, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof.These silver halides can be processed by various methods such as the ammonia method, the neutral method, the so-called convergence method, and the simultaneous mixing method. built.

In addition, gelatin and derivative gelatin such as phthalated gelatin and malonated gelatin are generally used as hydrophilic colloids for dispersing silver halide. Gum arabic, alginic acid, casein, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyatalylamide, imidized polyacrylamide, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used. Furthermore, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes include, for example, U.S. Pat.
No. 201, No. 2072908, No. 2739149
No. 294763, No. 2213995, No. 2493748, No. 2519001, West German Patent No. 929080, and British Patent No. 505979. C can be used alone or in combination of two or more, and if necessary, chemical sensitizers such as thioether compounds, quaternary ammonium salt compounds or polyalkylene oxide compounds, triazoles, imidazoles, azaindenes, etc. Stabilizers such as benzothiazolium compounds, zinc compounds, cadmium compounds, mercaptans, etc.; chromium salts, zirconium salts, mucochloric acid, Japanese Patent Publication No. 7133 of 1983, Japanese Patent Publication No. 1987-46-
No. 1872, U.S. Patent No. 682641, U.S. Patent No. 37
No. 36320, No. 3362827, No. 33252
No. 87, British Patent No. 686440, British Patent No. 133264
Hardeners such as aldehyde-based, triazine-based, polyepoxy compounds, active halogen compounds, triethylenebosamide-based, and ethyleneimine-based hardeners described in No. 7 specification; dihydroxy such as glycerin, 1,5-bentanediol, etc. Various photographic additives such as alkanes plasticizers; fluorescent brighteners; antistatic agents; and coating aids can be used alone or in combination of two or more, and the resulting silver halide The emulsion contains a dispersion of the compound represented by the general formula according to the present invention as described above, and if necessary, a subbing layer, an intermediate layer, and a protective layer are used to form a dispersion of cellulose acetate, cellulose nitrate, polycarbonate, etc. A silver halide color photographic light-sensitive material is obtained by coating on a support such as a synthetic resin film such as polyethylene terephthalate or polystyrene, baryta paper, polyethylene-coated paper, or a glass plate. The silver halide color photographic light-sensitive material according to the present invention can also be applied to an internal type silver halide color photographic light-sensitive material containing a coupler or an external type silver halide color photographic light-sensitive material containing a coupler in a developing solution. This is advantageous for internal silver halide color photographic materials, and it is advantageous to carry out color development by a color development method after exposure.

Furthermore, the coupler and the color developing agent are protected so that they do not come into contact with each other when unexposed and are present in the same layer, and can be used in silver halide color photographic light-sensitive materials that can come into contact with each other after exposure, or silver halide colors containing couplers. It is also applicable to silver halide color photographic materials in which a coloring agent is contained in a layer that does not contain the coupler in a photographic light-sensitive material, and when an alkaline processing solution is penetrated, the coloring developing agent is moved and can come into contact with the coupler. Furthermore, in a silver halide color photographic light-sensitive material for diffusion transfer, the compound according to the present invention can be added to the light-sensitive element and/or the image-receiving element of the light-sensitive material. is advantageous. In the reversal method, the image is developed with a black and white negative developer,
It is then exposed to white light or treated with a bath containing a fogging agent such as a boron compound, and further color developed with an alkaline developer containing a color developing agent. At this time, there is no problem even if a fogging agent is included in an alkaline developer containing a color developing agent. After color development, it is bleached with a bleaching solution containing ferricyanide or a ferric salt of aminopolycarboxylic acid as an oxidizing agent, and then fixed with a fixing solution containing a silver salt solvent such as thiosulfate to form a silver image. Removes the silver halide, leaving a dye image. Instead of using a bleaching solution and a fixing solution, bleach-fixing can also be carried out using a one-bath bleach-fixing solution containing an oxidizing agent such as a ferric salt of an aminopolycarboxylic acid and a silver salt solvent such as thiosulfate. Further, in combination with color development, bleaching, fixing, or bleach-fixing, various treatments such as prehardening, neutralization, water washing, termination, and stabilization may be performed. In particular, processing steps in which the silver halide color photographic light-sensitive material of the present invention is advantageously processed include, for example, color development,
The process includes washing with water, bleach-fixing, washing with water, stabilizing and drying as necessary, and this processing process is performed at, for example, 30°C.
It is carried out at higher temperatures and in an extremely short time. Typical treatment steps and typical compositions of each treatment liquid used are shown below. Treatment step (3'C) Add water to make 11, and add PHL using sodium hydroxide.
O. Adjust to 3O.

Add water to adjust to 11, and use ammonia water to pH 6.5.
Adjust to.

Add 8001 ni of water, add sodium acetate and adjust the pH to 3.
．． After adjusting to 5 to 4.0, water is further added to make it 11.

Particularly useful color developing agents used for color development of the silver halide color photographic light-sensitive material of the present invention include primary noenylene diamines, aminophenols and derivatives thereof. This can be cited as a representative example.

N,N-dimethyl-p-phenylenediamine, N,N-
Diethyl-p-phenylenediamine, N-carbamidomethyl-N-methyl-p-phenylenediamine, N-carbamidomethyl-N-tetrahydrofurfuryl-2-methyl-p-phenylenediamine, N-ethyl-N- Carboxymethyl-2-methyl-p-phenylenediamine, N
-Carbamidomethyl-N-ethyl-2-methyl-p-phenylenediamine, N-ethyl-N-tetrahydrofurfuryl-2-methyl-p-aminophenol 3-acetylamino-4-aminodimethyla)niline, N -Ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N-methyl-N-β-sulfoethyl-p- Salts of phenylenediamine with inorganic acids such as hydrochloric acid and sulfuric acid, or organic acids such as p-toluenesulfonic acid.

A silver halide color photographic light-sensitive material using the compound according to the present invention is processed using a color developing solution containing both a first aromatic amino color developing agent and an oxidizing agent that causes a redox reaction for the metallic silver image. is also valid.

When these color developing solutions are used, the color developing agent is oxidized by an oxidizing agent and then coupled with a photographic color coupler to form a dye image.

Such a color developing solution is disclosed, for example, in JP-A-48-9729, and the preferred oxidizing agent for this purpose is a cobalt complex salt having a coordination number of 6. Color photographic processing using such a color developer is particularly effective for so-called silver-saving color photographic materials, which have a smaller amount of silver than ordinary silver halide color photographic materials. Particularly useful cobalt complex salts include ethylenediamine, diethylenetriamine,
(1) at least two ethylenediamine ligands or (2) at least five amine ligands; or (3) at least one triethylenetetraamine ligand.

A particularly preferred cobalt complex salt is, for example, a complex salt represented by the following formula. In the above formula, En represents ethylenediamine, and X represents chloride, bromide, nitrite,
Represents at least one anion selected from nitrate, perchlorate, acetate, carbonate, sulfide, sulfate, hydrochloride, thiocyanate, isothiocyanate and hydroxide.

The most preferred complex salts are hexamine salts of cobalt, such as chlorides, bromides, sulfites, sulfates, perchlorates,
Nitrite and acetate. Cobalt complex salts used in color developing solutions are generally used in color developing solutions 1! about 0
．． More preferably, in a concentration range of 1 g to about 509, about 1 f
! 159 to about 159. Further, the silver halide color photographic light-sensitive material using the compound according to the present invention is developed in a color developer containing a primary aromatic amino color developing agent, and then preferably during the color development step. Amplify is received in the photosensitive layer and
using a color photographic processing method comprising the presence of a color developing agent transferred into a color photographing bath and brought into contact with an intensifier containing an oxidizing agent as described above, for example a cobalt complex having a coordination number of 6. is also useful.

Further, as another oxidizing agent preferable for this purpose, for example, an aqueous hydrogen peroxide solution disclosed in Japanese Patent Publication No. 53-28212 is also useful. It is preferable that the intensifying solution contains a silver halide development inhibitor in addition to the oxidizing agent to process the silver halide color photographic light-sensitive material. Then, the reinforcement process can be performed under indoor lighting. Following this approach, dye formation can be observed and stopped after the desired dye concentration is reached. Preferred development inhibitors are water-soluble bromide compounds such as potassium bromide, and heterocyclic compounds such as tetrazole, azaindene and triazole groups that do not contain mercapto or ionic iodide groups. The concentration of cobalt complex salt contained in the intensifying solution is generally about 0.29.
~ about 209/11 most preferably about 19 to about 159/l
The concentration of the hydrogen peroxide aqueous solution is generally about 0.01 to
10(f), most preferably 0.5-5%.

When a water-soluble bromide is used as a development inhibitor, the material generally has a concentration in the intensifier of about 19 to about 409
/l, while development inhibitors consisting of compounds having a heterocyclic structure are usually used in concentrations of about 0.01 to about 39/l. Reinforcing baths are generally used at a pH of 6-14, preferably 8-12. In addition to the above-mentioned development inhibitor, the intensifying solution may further contain a development accelerator, a stabilizer, a water softener, a thickening agent, an agent for preventing uneven processing, etc., if necessary.

The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Exemplary coupler (48) 409 and exemplary compound (self) 1
2f1 is dibutyl phthalate 40f! ethyl acetate 120
After dissolving in f1, it was added to 200 cc of 5(f) gelatin aqueous solution containing sabonin, and then dispersed with a homogenizer, and the resulting dispersion was mixed with green-sensitive silver chlorobromide (40 mol% silver chloride).
) Added to emulsion 350CC, coated on polyethylene coated paper and dried to obtain a silver halide color photographic light-sensitive material.This silver halide color photographic light-sensitive material was subjected to light wedge exposure according to a sensitometry method, and then described in this paper. After treatment according to the treatment method described above, irradiation was performed using a xenon fademeter for 20, 40, 60, and 80 hours, and the concentration after exposure (percentage of the concentration of O before exposure (DO)) was determined. /DO×
100) using a Sakura color densitometer PD-16 model (manufactured by Konishiroku Photo Industry Co., Ltd.), the dye fading rate was measured with green light, and the Y stain increase rate in the unexposed area was measured with blue light.

For comparison, 2,2,4-trimethyl-6-hydroxy-
Jyotosert-octylchroman (comparative sample pile), 3,
3,-Dimethyl-5-hydroxy-2-(N-methylanilino)-6-Tert-octoxycoumaran (comparative sample (9) is shown in the same amount), and 3-anilino-5 according to the present invention -3 instead of pyrazolone type coupler-
1-( is an acylamino-5-pyrazolone type coupler)
2,4-dimethyl-6-tacarophenyl-3-{3-[
The case where only α-(3-bentadecylphenoxy)butyramide]benzamide}-5-pyrazolone 389 is used (comparative sample []) is shown, and the case where exemplified compound 02) 129 is further used as the comparative sample [] (Comparative sample []) is also shown.

Note that the blank is for the example coupler (48) only.

The results are shown in Table 1.

From the results in Table 1, the blank of sample eyebrow 1 has a pigment fading rate of Y.
-The stain increase rate is also large.

Furthermore, although the dye fading rate and the Y-stain j increase rate are certainly small for samples rot 3 and rot 4, when the compound according to the present invention is used (sample taki 2), it becomes even smaller compared to the comparative sample. I understand. Furthermore, when a coupler other than the 3-anilino-5-pyrazolone type coupler according to the present invention is used, the effect of adding the compound represented by the general formula j according to the present invention can be seen, but the effect is not sufficient. However, it can be seen that when the compound represented by the general formula according to the present invention is combined with a 3-anilino-5-pyrazolone type coupler, the effect is even more pronounced. Instead of the above color developing solution, three concentrated solutions CA), (B), and (C) consisting of the following compositions are sequentially added, mixed, and dissolved in an appropriate amount of pure water, making the total amount 11. Even when the finished color developer was used, the same effect as above was obtained.

[Example 2 The exemplified compounds, exemplified couplers and solvents according to the present invention shown in Table 2-1 were dispersed in the same manner as in Example 1 in 500 cc of a 10% aqueous gelatin solution containing sodium dodecylbenzenesulfonate.

In addition, as a comparative compound, 6,6'-dihydroxy-7,
7'-di-n-octyl-4,4,4,4,-tetramethyl-bis2,2-spirocman (comparative compound pile), comparative compound is 2,2-(β,β-dimethyl)-bentamethylene-J Me[cyclohexyl-6-chromanol (comparative compound [I)], 2,2,4-trimethyl-6-hydroxy-
Jyoser[-octylutaroman (comparative compound (J[
l) was used.

After adding the dispersions of samples 1 to 20 in Table 2-1 to 300 cc of green-sensitive silver chlorobromide (silver chloride 30 mol%) emulsion, the samples were coated on polyethylene coated paper and dried.
I got it. These samples were subjected to light wedge exposure according to a sensitometric method, processed in the same manner as in Example 1, and the same photographic properties were determined by the same method.

The results are shown in Table 2-2. From the results in Table 2-2, it can be seen that the combination of the compound according to the present invention and the 3-anilino-5-pyrazolone type coupler provides excellent dye fading rate and Y-stain increase rate.

Example 3 Exemplary compound (self) 18.5f11 Exemplary coupler (46)
After dissolving 399 and 2,5-di-Tert-octylhydroquinone 1.99 in dibutyl phthalate 26f11 tricresyl phosphate 139 and ethyl acetate 1009, 200 CC of 5% gelatin aqueous solution containing saponin was added.
and dispersed with a homogenizer, and the resulting dispersion was added to green-sensitive silver chlorobromide (silver chloride 40 mol%) emulsion 35.
This A2-(2
1-Hydrotablet 3/57-di-tert-butylphenyl)benzotriazole 9f1 was dissolved in tritalesyl phosphate 109 and ethyl acetate 309, then added to a 10% gelatin aqueous solution containing saponin, dispersed with a homogenizer, and obtained. The resulting dispersion was coated so that the amount of ultraviolet absorber was 7 to 100 d, and dried, and the resulting silver halide color photographic light-sensitive material was designated as Sample (1).

Furthermore, sample (2) is a silver halide color photographic light-sensitive material that does not contain only an ultraviolet absorber in Sample (1), and a silver halide color photographic light-sensitive material that does not contain only the exemplary compound (self) that is a compound according to the present invention. is the sample (3),
As a comparative sample, a silver halide color photographic light-sensitive material containing no ultraviolet absorber and the compound according to the present invention was used as a comparative sample [D1] 2,2,4-trimethyl-6-hydroxy-J iodine instead of the compound according to the present invention. Comparative Sample I was a silver halide color photographic light-sensitive material using Ert-octyl-chroman. Furthermore, 1-(2,4,6-trichlorophenyl)-3-(2,4-di-Ter[-amylphenoxybutyramide)-5-pyrazolone] which is a force plastic other than the coupler according to the present invention Coupler 38θ
The case where only 18.5 fl of the exemplified compound aυ was added was defined as a comparative sample. The samples (1 (3)) and comparative samples [I], ULI, and Stir were exposed to light wedges according to the sensitometric method, treated in the same manner as in Example 1, and exposed to sunlight for 60, 100, 140, and 180 hours. The dye fading rate and the Y-stain increase rate in the unexposed area were measured and determined by the same method as in Example 1.

The results are shown in Table 3. From the results in Table 3, it can be seen that the greatest effect is obtained when the compound according to the present invention and the 3-anilino-5-pyrazolone type coupler coexist.

Example 4 Exemplified compound (5) 12.5f1 was converted to dibutyl phthalate 1
After dissolving in 1 fl ethyl acetate 30 fl, add 120 C of 5% gelatin aqueous solution containing sodium dodecylbenzenesulfonate.
After adding C, it is dispersed with a homogenizer, and the resulting dispersion is converted into a green-sensitive silver chlorobromide emulsion (silver chloride 30 mol%) 3
After adding the solution to 00 cc, it was coated on polyethylene coated paper and dried to obtain a silver halide photographic material.

This silver halide photographic light-sensitive material was subjected to light wedge exposure according to a sensitometric method, and then exposed to light at 24°C according to the following order.
treated at a temperature of

Processing solutions having the following formulations were used as the first developer, color developing solution, bleaching solution, and fixing solution.

Claims (1)

[Scope of Claims] 1 Contains a magenta dye formed using a 3-anilino-5-pyrazolone compound and a compound represented by the following general formula (provided that a compound represented by the following general formula (A) is further included) A color photographic material characterized by: General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3 and R_4 are alkyl groups having 1 to 18 carbon atoms,
and the total number of carbon atoms of R_4 is 32 or less, and
is a simple bond, an oxygen atom, a sulfur atom, a sulfonyl group, or ▲a mathematical formula, a chemical formula, a table, etc.▼, and R_5 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
n is an integer from 1 to 3. ) General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_2, R_3, and R_4 are hydrogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, aralkyl groups, aralkoxy groups, alkenyl group, alkenoxy group, acylamino group, halogen atom, alkylthio group, arylthio group, diacylamino group, acyl group, sulfonamide group, alkylamino group, alkoxycarbonyl group, and acyloxy group, which may be the same or different from each other. . A represents a nonmetallic atom necessary to complete a 5- or 6-membered ring together with >C=C'-O-. )