JPS6320337B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide color photographic light-sensitive material containing an aromatic primary amine color developing agent precursor, and more specifically, the present invention relates to a silver halide color photographic light-sensitive material containing an aromatic primary amine color developing agent precursor that improves color development and storage stability. The present invention relates to a silver halide color photographic material that is processed with an alkaline aqueous solution (hereinafter referred to as an activator) to obtain a dye image. Ordinary silver halide color photographic materials contain non-diffusible couplers that can react with oxidized products of aromatic primary amine color developing agents to form azomethine dyes and indoaniline dyes. A dye image can be obtained by processing with an alkaline color developing solution containing a color developing agent. On the other hand, if an aromatic primary amine color developing agent is incorporated into a silver halide color photographic light-sensitive material along with a non-diffusible coupler, color development can be carried out using an activator which is basically a simple alkaline aqueous solution. In fact, in silver halide black-and-white photographic light-sensitive materials, image forming systems are widely used in which a black-and-white developing agent is incorporated into the light-sensitive material and a silver image is obtained by subjecting the material to activator treatment. The advantages of the method of incorporating an aromatic primary amine color developing agent into a silver halide color photographic light-sensitive material and performing activator treatment include, first of all, the ability to perform color development with a high pH activator. This means that the development time can be significantly shortened compared to the conventional color development process at pH 10 to 11, which has been carried out due to the instability of aromatic primary amine color developing agents.Secondly, the development time can be significantly reduced. The minimum amount of aromatic primary amine color developing agent required for the silver halide and non-diffusive coupler in the light-sensitive material can be incorporated into the light-sensitive material, and it can be supplied directly into the light-sensitive material, eliminating waste. Thirdly, since color development is performed with an activator, aromatic primary amine color development is possible. Concerns about skin itching and rashes caused by color developing solutions containing developing agents, as well as the burden of waste liquid disposal, are significantly reduced, and handling at photo labs or in-house processing becomes easier. However, if an aromatic primary amine color developing agent is directly incorporated into a silver halide color photographic light-sensitive material, desensitization, fogging, and staining will occur significantly, so a technology for using it as an aromatic primary amine color developing agent precursor has not been developed. Are known. See, for example, U.S. Patent No. 3,342,599, Research Disclosure.
14850, 15159, and JP-A-54-9924, British Patent No.
No. 803783 describes phthalimide compounds of aromatic primary amine color developing agents and phthalic acids, and U.S. Pat. Regarding the compound in which the compound is protected with a urethane bond, US Pat. No. 3,719,492 describes a metal complex of an aromatic primary amine color developing agent and a water-soluble polyvalent metal salt. Originally, an aromatic primary amine color developing agent precursor (hereinafter referred to as "precursor") is used when incorporated into (manufactured) a silver halide color photographic light-sensitive material, and when it is incorporated into a silver halide color photographic light-sensitive material. It is preferable that the color developing agent be inert during storage without causing any influence, and when it comes into contact with an activator, immediately release the aromatic primary amine color developing agent and contribute to the formation of a dye image. As a result of studying the above-mentioned conventional technology, it was found that the precursor is unstable when it is incorporated into a photosensitive material or during storage of a photographic material in which a precursor is incorporated, so that silver halide color photographic materials cannot be used. On the other hand, the precursor is stable when it is incorporated or during the storage of the photographic material containing the precursor. but,
Since it is still inactive even when it comes into contact with an activator, it is difficult to obtain sufficient concentration and sensitivity, and therefore no preferred method has been found. Therefore, the first object of the present invention is to improve desensitization by incorporating silver halide into a color photographic light-sensitive material or preserving the incorporated light-sensitive material, and to improve the occurrence of fog and stain. It is an object of the present invention to provide a precursor that rapidly releases an aromatic primary amine color developing agent when contacted with beta. A second object of the present invention is to provide a halogenated dye that has high color density and sensitivity, has a built-in precursor that has improved desensitization during storage, and improved fogging and staining, and that forms a dye image by activator treatment. An object of the present invention is to provide a silver color photographic material. An object of the present invention is to provide a silver halide color photographic light-sensitive material containing an aromatic primary amine color developing agent precursor and a non-diffusible coupler, in which the aromatic primary amine color developing agent precursor is combined with a water-soluble polyvalent metal salt. This was achieved using a silver halide color photographic light-sensitive material which is a reaction product of an aromatic primary amine color developing agent and a water-soluble sulfite. The water-soluble polyvalent metal salt used in the present invention generates a polyvalent metal cation when dissolved in water, and is represented by the following general formula (). In the general formula () (M ^+m ) _p (X ^-n ) _np/o , M ⁺ is a polyvalent metal (e.g. cadmium, copper,
m is an integer of 2 or 3, p is an integer of 1 or 2, X ^- is an acid anion (e.g. halogen,
acetic acid, chloric acid, bromic acid, nitric acid, sulfuric acid, etc.), n is 1
or represents an integer of 2. The water-soluble polyvalent metal salt used in the present invention is preferably a divalent metal salt, and specific examples thereof include cadmium chloride, cadmium bromide, cadmium iodide, cadmium acetate, cadmium bromate, cadmium nitrate, and sulfuric acid. Cadmium salts such as cadmium, copper salts such as cupric chloride, copper bromide, copper acetate, copper chlorate, copper bromate, copper nitrate, copper sulfate, lead salts such as lead chloride, lead chlorate, lead acetate, Examples include zinc salts such as zinc chloride, zinc bromide, zinc iodide, zinc chlorate, zinc nitrate, zinc sulfate, and zinc acetate. The aromatic primary amine color developing agent used in the precursor of the present invention is described in the literature The Journal of American Chemical Society.
of American Chemical Society) Volume 73, 3100
-3125 (1951), and includes those represented by the following general formula (). General formula () In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, propyl group, β-hydroxyethyl group,
β-methoxyethyl group, β-methylsulfonamidoethyl group, hydroxymethyl group, etc.), and R ₁ and R ₂ are bonded to each other to form a nitrogen-containing saturated heterocycle (such as morpholyl group, piperidyl group,
3-hydroxypiperidyl group, piperazyl group, pyrrolidyl group, imidazolidyl group, pyrazolidyl group, etc.). _R3 , _R4 , _R5 and _R6
each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms (e.g., a methyl group, an ethyl group, a methylol group, etc.), a halogen atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and
3 represents an alkoxy group (eg, methoxy group, ethoxy group, etc.) or a carbamoyl group (eg, methylcarbamoyl group, etc.). Furthermore, aromatic primary amine color developing agents are generally stabilized by forming salts with acids (e.g. hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc.), but when used in the precursor of the present invention, There is nothing wrong with this salt state. Specific examples of the aromatic primary amine color developing agent used to synthesize the precursor of the present invention are shown below. The water-soluble sulfite used in the synthesis of the precursor of the present invention is a compound that releases a sulfite anion in an aqueous solution, and specific examples thereof include sodium sulfite, potassium sulfite, ammonium sulfite, and the like. The precursor of the present invention can be synthesized by the following method. The solvents for the water-soluble polyvalent metal salt, aromatic primary amine color developing agent, and water-soluble sulfite are those that can be dissolved at a certain temperature and a certain pH, and are water,
Ion-exchanged water is particularly preferred, and may contain a water-miscible organic solvent (for example, methanol, ethanol, acetone, dimethylformamide, dimethyl sulfoxide, ethylene glycol, benzyl alcohol, etc.) as an auxiliary solvent, and
It does not matter if it contains water-soluble polymeric substances (eg, gelatin, agar, polyvinyl alcohol, carboxymethyl cellulose, etc.). The pH of the solvent is basically higher than the pKa value (acid dissociation constant) of the primary amine of the aromatic primary amine color developing agent used, and is the pH at which the metal cations of the water-soluble polyvalent metal salt begin to form hydroxides. A range lower than this value is preferable, and therefore a range of pH 5 to 9 is usually appropriate, although it varies depending on the type of aromatic primary amine color developing agent and water-soluble polyvalent metal salt used. The reaction temperature is usually 0° to 100°C, preferably 20° to
It can be done at 80℃. Regarding the reaction order, it is advantageous to add a water-soluble sulfite to the coexistence of a water-soluble polyvalent metal salt and an aromatic primary amine color developing agent. a method of adding a mixture of a polyvalent metal salt and an aromatic primary amine color developing agent;
Alternatively, there is a method of adding a water-soluble polyvalent metal salt to the coexistence of an aromatic primary amine color developing agent and a water-soluble sulfite, or conversely, a method of adding an aromatic primary amine color developing agent to a water-soluble polyvalent metal salt. A method of adding a mixture of water-soluble sulfite and a water-soluble sulfite may also be used. After the reaction is completed, water-insoluble crystals as a precursor are usually obtained, which are separately washed with water, dried, and incorporated into a silver halide color photographic light-sensitive material. In the above reaction, metal sulfite may precipitate as a reaction by-product, but there is no need to remove it because it has little effect on the photographic properties of the silver halide color photographic light-sensitive material. Further, when a water-soluble polymer substance is contained in the reaction solvent, the reaction solution may be added as it is to the silver halide color photographic emulsion without separating the crystals. Examples of synthesis of the precursor of the present invention are shown below, but the present invention is not limited thereto. Synthesis example MC-1 Dissolve 28.8g of zinc sulfate heptahydrate in 300c.c. of water,
2-Methyl-4-(N,N
428 c.c. of a 10% by weight aqueous solution of (diethylamino)aniline monohydrochloride was added. Next, when 400 c.c. of an aqueous solution containing 18.9 g of anhydrous sodium sulfite was slowly added dropwise, it became cloudy, and after the addition was completed, it was washed with water and acetone and air-dried to obtain 31.8 g of white crystals. . MC-2 Using the method of MC-1, 2-methyl-4(N,
2-methyl-4-instead of 428 c.c. of a 10% by weight aqueous solution of
20% by weight aqueous solution of (N-ethyl, N'-β-hydroxyethylamino)aniline monosulfate 292 c.c.
Using this method, 3.11 g of crystals were obtained. MC-3 1.36 g of zinc chloride was dissolved in 70 c.c. of water, and while stirring at 50°C, 3.56 g of 2-methyl-4-(N,N-diethylamino)aniline was dissolved in 50 c.c. of water. A solution of 50° C. dissolved in methanol (1:1) mixed solvent was added, and a solution of 1.89 g of anhydrous sodium sulfite dissolved in 40 cc of water was slowly added dropwise thereto. After the dropwise addition was completed, the mixture was cooled, and the white crystals formed were separated, washed with water and acetone, and air-dried. The yield was 2.90g. MC-4 13g of photographic ossein gelatin, 0.4g of polyvinyl alcohol, and 2.88g of zinc sulfate heptahydrate to 100g
Dissolve in cc of water and further add 2-methyl-4-(N,
21.4 cc of a 20% by weight aqueous solution of N-diethylamino)aniline monohydrochloride was added and stirred at 40°C. When 3.8 cc of a 50% by weight aqueous solution of sodium sulfite was added dropwise, the mixture became cloudy. After the dropwise addition was completed, the mixture was cooled, set, and poured with ice water. The noodles were washed in step 1. MC-5 Copper sulfate pentahydrate 2.5 and 2-methyl-4-
(N,N-diethylamino)aniline monohydrochloride
Dissolve 4.28 g in 100 c.c. of water and stir at room temperature to add 40 g of an aqueous solution containing 1.89 g of anhydrous sodium sulfite.
After adding cc and cooling on ice, separate the obtained crystals, wash with water,
Dry. MC-6 Copper acetate monohydrate 2.0g and 2-methyl-4-
(N,N-diethylamino)aniline 3.56g 60
Dissolve in cc of water/ethanol (1:1) mixed solvent, stir at room temperature, and add anhydrous sodium sulfite.
A solution of 1.89 g dissolved in 40 c.c. of water was slowly added dropwise, and after the addition was complete, the obtained crystals were separated, washed with water, and dried. Among the above synthetic substances, MC-1, 2, 3, 4
The following shows elemental analysis values, quantitative values of aromatic primary amine color developing agent (oxidation-reduction titration method using ceric sulfate, which is often used in the industry), and quantitative values of metals by atomic absorption spectrometry. MC-1 Element Analysis value (%) Zn 21.2 C 34.0 H 5.3 N 7.2 S 10.2 Cl (not detected) Aromatic primary amine color developing agent 46.9 This is

It is estimated to be a mixture of [Formula] and 1.5 (ZnSO ₃ 2H ₂ O). MC-2 Element Analysis value (%) Zn 18.8 C 34.5 H 5.2 N 7.1 S 9.0 Cl (0.1% or less) Aromatic primary amine color developing agent 49.2 This is It is estimated to be a mixture of ZnSO ₃ and 1.2 (ZnSO 3 2.5H ₂ O). MC-3 Element Analysis value (%) Zn 20.0 C 34.7 H 5.3 N 7.1 S 9.8 Cl (0.1% or less) Aromatic primary amine color developing agent 47.2 This is

It is estimated to be a mixture of [Formula] and 1.4 (ZnSO ₃ 2H ₂ O). MC-4 A sample of noodles after washing with water was dissolved by heating, and after gelatin decomposition treatment with pronase, thorough washing with water, and drying, analysis was performed. Element Analysis value (%) Zn 20.7 C 34.6 H 5.4 N 7.0 S 9.9 Cl (0.1% or less) Aromatic primary amine color developing agent 45.1 This is

It is estimated to be a mixture of [Formula] and 1.5 (ZnSO ₃ 2H ₂ O). The precursor of the present invention may be contained in any hydrophilic colloid layer on the side of the silver halide emulsion layer containing the non-diffusible coupler on the support. Examples of the hydrophilic colloid layer include a protective layer, a silver halide emulsion layer, an intermediate layer, and a subbing layer, and the hydrophilic colloid layer may be contained in at least one of these layers. That is, the photographic light-sensitive material according to the present invention has a silver halide emulsion layer containing at least one non-diffusible coupler on at least one surface of a support, and a silver halide emulsion layer containing at least one non-diffusible coupler on the emulsion layer and/or on the side of the emulsion layer on the support. At least one of the hydrophilic colloid layers other than the emulsion layer provided
The layer contains the precursor of the present invention. In one embodiment of the invention, a red-sensitive silver halide emulsion layer containing a non-diffusible cyan coupler, a green-sensitive silver halide emulsion layer containing a non-diffusible magenta coupler, and a non-diffusible silver halide emulsion layer are provided on a support. In a multilayer color photographic material having a blue-sensitive silver halide emulsion layer containing a yellow coupler, the precursor of the present invention is contained in at least one of the hydrophilic colloid layers adjacent to at least one of the emulsion layers. can be mentioned. The support used in the photographic material of the present invention is
Any support used as a support for ordinary silver halide photographic light-sensitive materials can be used. Examples include cellulose acetate film, polyethylene terephthalate film, polystyrene film, polycarbonate film, or laminates thereof, paper, baryta paper, paper coated with α-olefin polymer, synthetic paper, glass, and the like. In the photographic material of the present invention, it is advantageous to use gelatin as the binder or protective colloid, but other hydrophilic colloids such as
Gelatin derivatives, graft polymers of gelatin and other polymers, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfate esters, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, Various synthetic hydrophilic polymeric substances such as single or copolymers of polymethacrylic acid, polyacrylamide, etc. can be used. The silver halide emulsion used in the photographic light-sensitive material of the present invention includes not only silver chloride, silver bromide, and silver iodide, but also mixed silver halides, such as silver chlorobromide, silver iodobromide, silver chloroiodide, and silver chloride. Silver iodobromide etc. can be applied. These silver halide emulsions can be produced by conventional methods, such as an ammonia method, a neutral method, an acid method, a halogen conversion method, a function addition method, and a homogeneous precipitation method. Although the average diameter of the grains is not limited, it is preferably from 0.01 .mu.m to 5 .mu.m. Alternatively, two or more types of silver halide emulsions formed separately may be used as a mixture. The silver halide emulsion used in the photographic material of the present invention can be chemically sensitized using a conventional method. In other words, gold sensitization using gold complex salts, reduction sensitization using reducing substances, sulfur sensitization using compounds containing sulfur that can react with silver ions, or so-called activated gelatin, and noble metals belonging to group 3 of the periodic table. A sensitization method using a salt of can be used. The silver halide emulsion used in the photographic light-sensitive material of the present invention can be subjected to spectral sensitization. As a method, cyanine pigments such as monomethine cyanine, pentamethine cyanine, merocyanine, and carbocyanine are used alone or in combination.
Alternatively, they can be combined with styryl dyes, aminostilbene compounds, etc. In the photographic material of the present invention, known stabilizers and antifoggants can be used, and in addition, known surfactants, antifoaming agents, antistatic agents, hardeners, film property improvers, and brighteners. , anti-staining agents, ultraviolet absorbers, anti-irradiation dyes, and other additives may be included. When a cross oxidizing agent is used in the photographic light-sensitive material of the present invention, color development is improved. Cross-oxidizing agents are well known in the art, and include p-aminophenol compounds, p-phenylenediamine compounds, phenidone derivatives, and the like. Generally, these compounds are black-and-white developers that develop the exposed silver halide, but the resulting oxidation products do not couple with the coupler but rather oxidize the aromatic primary amine color developing agent. This is a substance that once again has the ability to develop. On the other hand, the oxidized aromatic primary amine color developing agent reacts with the coupler to form a dye. The amount of the cross-oxidizing agent added to the photographic light-sensitive material of the present invention is the total amount of silver halide on the same area.
The range is preferably from 0.01 to 2 moles. All known non-diffusive couplers can be used in the photographic material of the present invention. That is,
Yellow couplers, magenta couplers and cyan couplers can be used in appropriate combinations depending on the purpose. Yellow couplers include beizoylacetanilide compounds and pivaloylacetanilide compounds; magenta couplers include 5-pyrazolone compounds, pyrazolotriazole compounds, pyrazolinobenzimidazole compounds, indazolone compounds, and cyanoacetyl compounds; cyan couplers include These include phenol compounds, diacylaminophenol compounds, and naphthol compounds. Furthermore, the non-diffusible coupler used in the photographic light-sensitive material of the present invention is a so-called two-equivalent type active point substituted coupler in which the carbon atom at the coupling position is substituted with a substituent that can be released during the coupling reaction. It's okay. Furthermore, the non-diffusible coupler used in the photographic material of the present invention has a fluorine-containing substituent for adjusting the color tone of the dye formed by reacting with the oxidized product of the aromatic primary amine color developing agent. You can also do that. The method for incorporating the precursor according to the present invention into a silver halide color photographic light-sensitive material is not particularly limited, and methods used in the art for couplers and other additives can be used. . For example, an oil protection method using a high boiling point solvent, a method of dissolving and dispersing in a water-miscible organic solvent,
Method of adding powder and dispersing with colloid mill,
Alternatively, a method of impregnating and dispersing in a polymer, latex, etc. can be used. The amount of the precursor according to the present invention is suitably in the range of 0.1 to 10 moles per mole of total silver halide on the same area of the silver halide color photographic light-sensitive material. Depends on the characteristics and type of coupler. The development of the silver halide color photographic light-sensitive material of the present invention is carried out in a conventional color development processing system using an activator bath instead of a color development bath, and other processing steps such as stopping, bleaching, fixing, bleach-fixing, For water washing, stabilization, etc., methods known in the photographic industry can be used as they are, in an appropriate combination, or with some of them omitted, depending on the purpose. The activator used in the development of the photographic material of the present invention is basically an alkaline aqueous solution, and is an aqueous solution of an inorganic base such as sodium hydroxide, potassium hydroxide, or sodium carbonate. These activators include color development accelerators such as benzyl alcohol, dimethylformamide, etc.
Preservatives such as hydroxylamine, triethanolamine, and inorganic and organic antifoggants such as potassium bromide, 5-methylbenzotriazole, and the like may also be included. It is also possible to include the cross-oxidizers mentioned above. Further, inorganic or organic salts can be included in order to provide the activator with a buffering effect or appropriate ionic strength. The pH of the activator may be alkaline, but it is preferably 9 or more, preferably 11 or more in order to quickly develop the silver halide. The temperature of the activator varies depending on the type of coupler, the type of cross-oxidizing agent, and the characteristics of the silver halide, but is usually 15 to 50°C, preferably 20 to 40°C. The precursor of the present invention significantly improves the stability of the compound described in U.S. Pat. No. 3,719,492 by introducing sulfite ions into the compound.
It also has the characteristics of producing a silver halide color photographic light-sensitive material that has good color development properties, almost no desensitization, and almost no fogging or staining. It hasn't been touched upon very much. The stability of the precursor of the present invention in silver halide color photographic light-sensitive materials is surprising, and contains substances other than sulfite ions, such as sulfate ions, carbonate ions, nitrate ions, nitrite ions, phosphate ions, Phosphite ion, hypophosphite ion, oxalate ion, silicate ion, metasilicate ion, etc. have no eye-catching effect. Examples of the present invention are shown below, but the present invention is not limited thereto. EXAMPLE On a polyethylene laminated paper support,
A green-sensitive silver halide emulsion layer containing magenta coupler (a) was provided, and a gelatin protective layer was provided thereon.
The coating amounts of coupler, silver halide, gelatin and other major additives are as follows. Sample-A (green-sensitive layer) Silver chloride (converted to silver) 0.3 g/m ² Magenta coupler (a) 0.4 g/m ² Ossein gelatin 2.5 g/m ² Phenidone derivative (b) 50 mg/m ² Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) 6 mg/m ² Hardener (c) 40 mg/m ² (gelatin protective layer) Ossein gelatin 1.1 g/m ² Alkanol B 4 mg/m ² Hardener (c) 20 mg /m ² magenta coupler (a) Phenidone derivative (b) Hardener (c) Sample-B (green-sensitive layer) 2-methyl-4 was added to the coating solution with the same composition as Sample-A.
-(N,N-diethylamino)aniline monohydrochloride was added. 2-Methyl-4-(N,N-diethylamino)aniline monohydrochloride 0.3 g/m ² The coating amounts of silver halide, coupler, gelatin and other additives were the same as Sample-A. (Gelatin protective layer) Same as sample-A. Sample-C (green-sensitive layer) Comparative compound MC was added to the coating solution with the same composition as Sample-A.
-X was added and dispersed using a colloid mill. MC-X 0.34 g/m ² (Synthesis method of comparative compound MC-X) Dissolve 1.36 g of zinc chloride in 50 c.c. of ethanol,
2-Methyl-4-(N,N
- When 35.6 cc of a 10 wt% ethanol solution of (diethylamino)aniline was slowly added dropwise, a white cloud appeared. After the addition was completed, the crystals were cooled on ice for about 10 minutes, and the resulting crystal circles were separated, washed with methanol, and air-dried. . yield
0.85g Element Analysis value (%) Zn 12.9 C 52.1 H 7.6 N 11.3 S (not detected) Cl 14.5 Aromatic primary amine color developing agent 70 This is

It is estimated that [Formula]. The coating amounts of silver halide, coupler, gelatin, and other additives are the same as in Sample-A. (Gelatin protective layer) Same as sample-A. Sample-D (Green Sensitive Layer) Compound MC-1 of the present invention was added to a coating solution having the same composition as Sample-A, and dispersed using a colloid mill. MC-1 0.53 g/m ² The coating amount of silver halide, coupler, gelatin and other additives is the same as Sample-A. (Gelatin protective layer) Same as sample-A. Sample-E (green-sensitive layer) Same as sample-A. (Gelatin protective layer) Compound MC-1 of the present invention was added to a gelatin coating solution having the same composition as Sample-A, and dispersed using a colloid mill. Sample-F (green-sensitive layer) The compound of the present invention was added to a coating solution with the same composition as Sample-A.
MC-2 was added and dispersed using a colloid mill. MC-2 0.53 g/m ² The coating amount of silver halide, coupler, gelatin and other additives is the same as Sample-A. (Gelatin protective layer) Same as sample-A. The above samples A to F were exposed to light at 500 CMS for 0.5 seconds using a sensitometer using a step wedge, and then samples B, C, D, E and F were subjected to the following treatment. Activator bath 30°C 1 minute Bleach-fix bath 40°C 1 minute Water washing 20°C 3 minutes However, the composition of each treatment solution is as follows. <Activator liquid> Benzyl alcohol 10ml Potassium carbonate 20g Potassium bromide 0.1g Add water to make 1. (PH11.8) <Bleach-fix solution> Iron ammonium ethylenediaminetetraacetate 61g Diammonium ethylenediaminetetraacetate 5g Ammonium thiosulfate 13.3g Anhydrous sodium sulfite 2.7g Add aqueous ammonia and water to make 1. (PH7.0) Since sample A does not contain an aromatic primary amine color developing agent precursor, a color developing solution having the following composition was used instead of the activator solution. <Color developer> 2-Methyl-4-(N,N-diethylamino)aniline monohydrochloride 2g Benzyl alcohol 10ml Potassium carbonate 20g Potassium bromide 0.1g Add water to make 1. (PH11.8) The results of the obtained samples A to G immediately after application and the results of the forced deterioration storage test are shown in Tables 1 and 2.

【table】

[Table] As is clear from Tables 1 and 2, the silver halide color photographic light-sensitive material incorporating the precursor of the present invention has good coloring properties, little fogging, and little desensitization due to storage, making it an excellent material. It can be seen that it is something that

Claims (1)

[Claims] 1. In a silver halide color photographic light-sensitive material containing an aromatic primary amine color developing agent precursor and a non-diffusible coupler, the aromatic primary amine color developing agent precursor contains a water-soluble polyvalent metal salt and an aromatic primary amine. A silver halide color photographic material characterized by being a reaction product of a color developing agent and a water-soluble sulfite.