JPS6325653B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a dye image, and more specifically, the present invention relates to a method for forming a dye image, and more specifically, an aromatic primary amine color developing agent, a salt thereof, or a schizophrenic base thereof is incorporated into a silver halide color photographic light-sensitive material, and an alkaline activation bath (hereinafter referred to as an activator) is incorporated. The present invention relates to a method of forming a dye image by processing a silver halide color photographic light-sensitive material with improved color development and storage stability. A general method for forming a dye image in a silver halide color photographic light-sensitive material is to form a light-sensitive material in the presence of a coupler that has the ability to react with an oxidized product of an aromatic primary amine color developing agent to form a dye. This is a method for obtaining azomethine or indoaniline dyes by developing with an aromatic primary amine color developing agent. Usually, an aromatic primary amine color developing agent is dissolved in an alkaline aqueous solution and used as a color developing solution, but this color developing solution is unstable against air oxidation and deteriorates over time. It changes the sensitivity and gradation of silver halide color photographic materials, and causes an increase in fog and stain. It is also well known that the waste liquid of the color developer, including the various additives added to maintain its stability, is undesirable from the viewpoint of pollution. In addition, the technology of incorporating an aromatic primary amine color developing agent into a silver halide color photographic light-sensitive material and performing color development using an activator has been studied for some time, and numerous reports have been made. When incorporating a group primary amine color developing agent, it is often used in the form of a precursor, taking into account its influence on silver halide and various additives. As a precursor of such an aromatic primary amine color developing agent, for example, US Pat. No. 3,342,599;
Research Disclosure 14850, 15159, JP-A-Sho
No. 54-9924 describes a Schiff base of an aromatic primary amine color developing agent and an aromatic aldehyde, and U.S. Patent No. 3719492 describes a reaction product of an aromatic primary amine color developing agent and a metal complex. , British Patent No. 803,783 describes a phthalimide compound of an aromatic primary amine color developing agent and phthalic acids, and U.S. Pat. Urethane compounds with aromatic primary amine color developing agents are described respectively. However, as a result of examining the above methods, it has become clear that not only are they unable to obtain sufficient color density, but also that desensitization, fogging, and staining occur significantly when silver halide color photographic materials are stored. Summer. Furthermore, this may be due to the unreacted products in the precursors being incorporated into silver halide color photographic light-sensitive materials during the process of incorporating them into silver halide color photographic light-sensitive materials, or during storage after incorporating them.
It has been found that liberated aromatic primary amine color developing agents or their oxidized products have an adverse effect on silver halide, non-diffusible couplers, and various additives in silver halide color photographic light-sensitive materials. It was done. We conducted further research and found that, surprisingly, when using aromatic primary amine color developing agents that are significantly inert compared to conventional aromatic primary amine color developing agents, such additives We have discovered the fact that there is no negative effect on The present invention has been made based on such knowledge. An object of the present invention is to provide a high color density even when an aromatic primary amine color developing agent, a salt thereof, or a schizophrenic base thereof is incorporated into a silver halide color photographic light-sensitive material, and to reduce the color density even when the light-sensitive material is stored. It is an object of the present invention to provide a method for forming a dye image with extremely low occurrence of blur, fog, and stain. 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, a salt thereof, or its Schiff base and a non-diffusible coupler. In the method of forming a dye image by processing with an activator in the presence of an oxidizing agent (hereinafter referred to as a cross-oxidizing agent), an aromatic primary amine color developing agent represented by the following general formula, or a salt thereof or This was achieved by using the Schiff base (hereinafter referred to as the compound of the invention). general formula In the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, halogen atoms (e.g. F, Cl, Br, I, etc.), alkyl groups (e.g. methyl groups, ethyl groups, etc.), alkoxy groups (e.g. methoxy groups). , ethoxy group, etc.), and Z represents a group of nonmetallic atoms necessary to form a 5- to 7-membered nitrogen-containing saturated heterocycle (for example, morpholyl group, piperidyl group, 3-hydroxypiperidyl group, piperazyl group, pyrrolidyl group). group, imidazolidyl group, pyrazolidyl group, etc.), but it is preferably a nonmetallic atomic group forming a 6-membered ring. Examples of the aromatic primary amine color developing agent of the present invention are shown below. Furthermore, the compounds of the present invention include salts with inorganic acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, nitric acid, etc.);
Organic acids or their derivatives (e.g. organic sulfonic acids, organic carboxylic acids, organic boric acids, organic sulfamic acids, organic sulfinic acids, organic hydroxamic acids, organic sulfohydroxamic acids, polymeric sulfonic acids, strong acid phenols, phosphoric acid esters, sulfuric esters) , thiosulfate S-ester, etc.),
Mention may be made of salts with metal complexes (eg metal complexes of nickel, zinc, lead, cadmium, copper, cobalt, etc.) or Schiff bases (preferably condensates with aromatic aldehydes). Examples of each are shown below, but are not limited to these. The compound of the present invention was published in the Journal of the American
Chemical Society, 73, 3100 (1951),
Photographic Science and Engineering
vol.8, No.3 (1964) or Research
As described in Disclosure 15167 and the like, it is characterized in that its developing ability for exposed silver halide is significantly lower than that of commonly used aromatic primary amine color developing agents. That is, the compound of the present invention cannot substantially develop exposed silver halide by itself, and can only become an oxidant by reacting with an oxidant of a cross-oxidizing agent. It is. Here, as a technology similar to the present invention, Japanese Patent Laid-Open No. 54
Publication No. -79035 discloses a technique in which a compound having a -NHCOOCH ₂ CH ₂ CN group is incorporated into the benzene nucleus of an aromatic primary amine. Limited to those having a membered nitrogen-containing saturated heterocyclic group, and
They differ in that they require the presence of a cross-oxidizing agent. It should be clearly stated that the object of the present invention can be achieved only by adopting such a configuration, and that it is a different invention from the above-mentioned known invention. When the compounds of the present invention are used in Schiff-based form, US Pat.
Preferably, water-soluble metal salts (eg copper sulfate, copper nitrate, zinc sulfate, etc.) are added as described in No. 3,719,492. The case where the aromatic primary amine color developing agent of the present invention is incorporated into a silver halide color photographic light-sensitive material is well known in the photographic industry as the case where a non-diffusible coupler is incorporated. An oil protection method using a high boiling point solvent, a method of dissolving and dispersing in a water-miscible organic solvent, or a method of dispersing in a polymer, latex, etc. are used. If the compound of the present invention is water-soluble, it may be incorporated as an aqueous solution, and the means for incorporating it is not particularly limited. Further, it may be incorporated in a photosensitive layer containing silver halide or in a subbing layer, intermediate layer, or protective layer that does not contain silver halide, but the latter layer that does not contain silver halide is preferred. The amount of the compound of the present invention added 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. It depends on the type etc. The cross-oxidizing agents used in the present invention are well known in the photographic industry, and include p-aminophenol compounds, p-phenylenediamine compounds, phenidone derivatives, etc. Generally, these compounds are suitable for black and white development. It is an agent that develops exposed silver halide, but the resulting oxidation product does not couple with the coupler, but oxidizes the aromatic primary amine color developing agent and regains its developing ability. It is a substance. On the other hand, the oxidized aromatic primary amine color developing agent reacts with the coupler to form a dye. In the present invention, the cross-oxidizing agent is preferably incorporated into the silver halide color photographic light-sensitive material, but it may be added to the activator. When incorporated into a silver halide color photographic light-sensitive material, the amount of the cross-oxidizing agent used in the present invention is in the range of 0.01 to 2 moles per mole of total silver halide on the same area. Preferably, when added to the activator, the amount is preferably in the range of 1×10 ⁻⁵ to 1×10 ⁻² mol/. Preferred cross-oxidizing agents for use in the present invention are 3-pyrazolidone derivatives, examples of which are shown below. The development of the silver halide color photographic light-sensitive material of the present invention is carried out using an activator instead of a color development bath in a conventional color development processing system, and other processing steps such as stopping, bleaching, fixing, bleach-fixing, and water washing are carried out. For stabilization and the like, 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 treatment liquid in the activator used in 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. It can also include. 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 processing solution in the activator may be alkaline, but it is preferably 9 or higher in order to promptly develop the silver halide.
The temperature of the activator varies depending on the type of coupler, the type of cross-oxidizing agent, and even the characteristics of the silver halide, but is usually 15 to 50°C, preferably
The temperature is 20-40℃. As the support used in the present invention, all those used as supports 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. The silver halide emulsion used in the present invention includes silver chloride, silver bromide, silver iodide, mixed silver halide,
For example, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloroiodobromide, etc. can be used. 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. The average diameter of the particles does not matter, but
It is preferably 0.01 μm to 5 μm, or two or more types of silver halide emulsions formed separately may be mixed and used. The silver halide emulsion used in 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 present invention can be subjected to spectral sensitization. The method is
Cyanine dyes such as monomethine cyanine, pentamethine cyanine, merocyanine, and carbocyanine can be used alone or in combination, or they can be used in combination with styryl dyes or aminostilbene compounds. Known stabilizers and antifoggants can be used in the silver halide emulsion used in the present invention.
Furthermore, known surfactants, antifoaming agents, antistatic agents,
Additives such as hardeners, film property improvers, brighteners, anti-staining agents, and ultraviolet absorbers can be included. All known non-diffusible couplers can be used in the present invention. That is, yellow couplers, magenta couplers, and cyan couplers can be used in appropriate combinations depending on the purpose. Examples of yellow couplers include benzoylacetanilide compounds and bivaloylacetanilide compounds; examples of magenta couplers include 5-pyrazolone compounds, pyrazolotriazole compounds, pyrazolinobenzimidazole compounds, indazolone compounds, and cyanoacetyl compounds; examples of cyan couplers include phenols. compounds, diacylaminophenol compounds, naphthol compounds, etc. Further, the coupler used in the present invention may be a so-called 2-equivalent type active site substituted coupler in which the carbon atom at the coupling position is substituted with a substituent that can be released during the coupling reaction. Moreover, the coupler used in the present invention is
It can also have 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 of the present invention. Further, in the silver halide color 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 and grafts of gelatin and other polymers may also be used. polymer, hydroxyethylcellulose, carboxymethylcellulose,
Various synthetic hydrophilic materials such as cellulose derivatives such as cellulose sulfates, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, etc. Polymeric substances and the like can be used. Examples of the present invention will be shown below, but the present invention is not limited thereto. EXAMPLE On a polyethylene laminated paper support,
a blue-sensitive silver chloride emulsion layer containing yellow coupler a;
Sample A was prepared by coating a total of six layers: a gelatin first intermediate layer, a green-sensitive silver chloride emulsion layer containing magenta coupler b, a gelatin second intermediate layer, a red-sensitive silver chloride emulsion layer containing cyan coupler c, and a gelatin protective layer. ~I made F. The coating amounts of silver halide and each coupler in each photosensitive layer are as follows. [Silver halide coating amount Coupler coating amount (g/m ² converted to silver) (g/m ² ) Blue-sensitive layer 0.35 0.37 Green-sensitive layer 0.30 0.41 Red-sensitive layer 0.25 0.41] Structural formulas of couplers a, b, and c above is shown below. For samples A to F, a compound shown in Table 1 was used as an aromatic primary amine color developing agent or a salt thereof, or a schizophrenic base thereof, and the exemplified compound PY-3 was used as a cross-oxidizing agent. For 1 mole of silveride, the former is the equivalent molar amount,
The latter is added in an amount of 0.15 mol, respectively 60 to the first intermediate layer.
%, and was divided into the second intermediate layer at a rate of 40% and incorporated.

【table】

[Table] In the table, compounds A, C and E were incorporated as aqueous solutions, compounds B, D and F were incorporated using the oil protection method, and the cross oxidizing agent was incorporated as an aqueous solution. After exposing samples A to F using a sensitometer (500 CMS, 0.5 seconds), the following treatments were performed. Activator 30°C 1 minute Stop 20°C 15 seconds Bleach-fixing 40°C 1 minute Washing 20°C 4 minutes However, the composition of each processing solution is as follows. <Activator treatment solution> Benzyl alcohol 10ml Potassium carbonate 20g Potassium bromide 0.1g Add water to make 1 (PH11.8) <Stop solution> Glacial acetic acid 20ml Add water to make 1 (PH3.8) <Bleaching Fixer> 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) Immediately after application of the obtained samples A to F The results and the results of the forced deterioration storage test are shown in Table 2.

[Table] In the table, R represents a red-sensitive layer, G represents a green-sensitive layer, and B represents a blue-sensitive layer. *For forced deterioration storage test, the coated sample is kept at a temperature of 50℃ and humidity.
After being left in an 80% atmosphere for 48 hours, it was exposed and developed. **The increase in fog is the value obtained by subtracting the fog value immediately after application from the fog value after the forced aging storage test. *** Density reduction is the density value that an exposed area with a density of 1.0 immediately after coating shows after a forced deterioration storage test, and is a model representation of photographic sensitivity. As is clear from Tables 1 and 2, the silver halide color photographic light-sensitive materials (samples A to C) containing the compounds of the present invention have less fog and excellent color development, and also exhibit desensitization, increased fog, and staining during storage. It can be seen that it is of excellent quality.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material containing an aromatic primary amine color developing agent, or a salt thereof or a Schiff base thereof, and a non-diffusible coupler. In the method of forming a dye image by processing with an alkaline activating bath in the presence of a cross-oxidizing agent, the aromatic primary amine color developing agent is represented by the following general formula: Method of forming dye images. general formula In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group,
Z represents a group of nonmetallic atoms necessary to form a 5- to 7-membered nitrogen-containing saturated heterocycle.