JPH0518102B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material in which the color forming properties of couplers are improved. Prior art and its problems Silver halide color photographic materials are usually produced using an aromatic primary amine color developing agent in the presence of a cyan coupler, a magenta coupler, and a yellow coupler after imagewise exposure. Color development processing is performed. At this time, the exposed silver halide grains of the silver halide color photographic light-sensitive material are reduced by the color developing agent, and the oxidized product of the color developing agent produced at the same time undergoes a coupling reaction with the coupler to form a cyan dye, Forms a color photographic image consisting of magenta and yellow dyes. In this method, a so-called internal color development method in which a coupler is previously included in a silver halide emulsion layer is widely used. The cyan, magenta, and yellow couplers used in this internal color development method must be fixed in silver halide emulsion layers that are selectively sensitive to blue, green, and red light, respectively, to prevent color mixing of the dyes. Therefore, these couplers have a long-chain aliphatic group in the molecule as a diffusion-preventing group. Since such couplers have lipophilic diffusion-preventing groups, they are usually dissolved in a high-boiling organic solvent and then dispersed in an aqueous gelatin solution as colloidal particles in the form of oil droplets. Silver halide color photographic light-sensitive materials containing couplers having such lipophilic groups have a slow color development rate due to the slow penetration of the color developing agent into the coupler.In order to speed up this, various penetrants have been investigated. and is used. Among them, benzyl alcohol is widely used as such a penetrating agent, and when processed with a color developing solution containing this, good coupler color development can be obtained, and the sensitivity, gradation, maximum density, etc. can be improved. Color photographic images with good photographic performance can be obtained. However, even when this benzyl alcohol is used, the coupler used rarely undergoes a complete color reaction in the highest concentration range, and in most cases, a sufficient amount of oxidized color developing agent is present in some couplers. However, it remains as a so-called dead coupler without contributing to color development. Therefore, in order to obtain sufficient dye density, it is necessary to use more coupler than necessary, which increases production costs and reduces the amount of gelatin used when producing color photographic materials. This increase makes high-speed coating difficult, or causes problems such as discoloration of uncolored areas of color photographic materials after processing due to heat, humidity, and light. In order to solve the above-mentioned problems, research has been carried out to develop couplers with high coloring properties to be included in silver halide color photographic materials. For example, JP-A-58-42045 and JP-A No. 58-42045
No. -95346 discloses a novel coupler with high color development. However, even when these couplers are used, dead couplers remain and cause capri or discoloration in uncolored areas after processing. On the other hand, in order to develop color photographic materials with a color developing solution containing benzyl alcohol and obtain good color development, this benzyl alcohol should be contained in 10 ml to 15 ml or more per color developing solution. However, because benzyl alcohol has low solubility in water, a considerable amount of polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin, and triethanolamine are usually added as cosolvents. It was necessary to solubilize the benzyl alcohol. By the way, benzyl alcohol and polyhydric alcohols have BOD (biochemical oxygen demand)
From the viewpoint of environmental pollution, it is desirable to reduce the use of benzyl alcohol as much as possible or not to use it at all, especially since it has a high pollution load value such as COD (Chemical Oxygen Demand) and COD (Chemical Oxygen Demand). If possible, the use of polyhydric alcohols as co-solvents can also be avoided, which has the secondary advantage of reducing the pollution load. For this reason, there is a photographic processing method or silver halide color in which silver halide color photographic light-sensitive materials are color-developed using a color-developing solution that contains as little benzyl alcohol as possible or does not contain benzyl alcohol at all, and which does not impair the color-forming properties of couplers. The development of photographic materials is desired, and research is being carried out for this purpose. For example, Japanese Patent Application Laid-Open No. 58-50536 discloses that a photosensitive material containing 1-aryl-3-pyrazolidone is prepared by adding benzyl alcohol at 2 to 8 ml per color developing solution.
It is proposed to process by adding ml. However, with the technology described in this publication,
It is not possible to improve color development, and there is no improvement in terms of dye density for a given amount of developed silver, and this drawback is particularly large in the middle density region of the characteristic curve. Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and the first object of the present invention is to improve the color development of the coupler, reduce the amount of residual dead coupler, and use the minimum amount of coupler necessary. An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material capable of obtaining high dye density. The second object of the present invention is that even when processed with a color developing solution that does not contain benzyl alcohol at all or contains only a small amount of benzyl alcohol,
An object of the present invention is to provide a method for processing a silver halide color photographic material that provides high dye density and good gradation. A third object of the present invention is to provide a method for processing silver halide color photographic materials in which the formation of leuco dyes is suppressed even when bleach-fixing is performed subsequent to color development. DETAILED DESCRIPTION OF THE INVENTION The above object of the present invention is to imagewise expose a silver halide color photographic light-sensitive material and then subject it to color development treatment in the presence of at least one of the compounds represented by the following general formulas [] and []. This is achieved by a method for processing silver halide color photographic materials characterized by the following. General formula [] R ₁ -O-R ₂ General formula [] R ₃ -O(-CH ₂ )- _o O-R ₄ (wherein R ₁ and R ₂ represent an alkyl group,
Further, R ₃ and R ₄ each represent an alkyl group, and n represents 2 or 3. ) R ₁ and R ₂ in the above general formula [] are preferably linear or branched alkyl groups having 1 to 20 carbon atoms, which may be the same or different, for example,
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-hexyl group, n-heptyl group, n
-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, n-heptadecyl group,
n-octadecyl group, etc. In addition, the above R ₁ ,
The total number of carbon atoms in the alkyl group represented by R ₂ is more preferably 8 to 32. R ₃ and R ₄ in the above general formula [] each preferably represent a straight chain or branched alkyl group which may be the same or different, and more preferably a methyl group having 1 to 20 carbon atoms, ethyl group, n
-propyl group, n-butyl group, n-hexyl group,
n-octyl group, 2-ethyl-hexyl group, n-
These include decyl group, n-dodecyl group, n-octadecyl group, and the like. These alkyl groups may be substituted with a phenyl group, and this phenyl group may be further substituted with a straight-chain or branched alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an iso-propyl group,
t-butyl group, etc.), an alkoxy group having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, etc.), and the number of carbon atoms in the alkyl group represented by R ₃ and R ₄ The total sum is preferably 9 to 32. Here, when the alkyl groups of R ₃ and R ₄ are substituted with a phenyl group, the alkyl groups of R ₃ and R ₄ are preferably a methyl group or an ethyl group. Specific examples of compounds represented by the general formula [] or [] used in the present invention are shown below, but the present invention is not limited to these compounds. Exemplary compound E-1 (n) C ₅ H ₁₁ -O- (n) C ₅ H ₁₁ E-2 (n) C ₆ H ₁₃ -O- (n) C ₆ H ₁₃ E-3 (n) C ₈ H ₁₇ -O-(n)C ₈ H ₁₇ E-5 (n)C ₁₀ H ₂₁ -O-(n)C ₁₀ H ₂₁ E-6 (n)C ₁₂ H ₂₅ -O-(n)C ₁₂ H ₂₅ E-7 (n)C ₁₄ H ₂₉ -O-(n)C ₁₄ H ₂₉ E-8 (n)C ₁₆ H ₃₃ -O-(n)C ₁₆ H ₃₃ E-9 CH ₃ -O-(n)C ₁₄ H ₂₉ E-10 (t )C ₄ H ₉ -O-(n) C ₁₀ H ₂₁ E-11 (n) C ₄ H ₉ -O-(n) C ₈ H ₁₇ E-12 (n) C ₄ H ₉ -O-(n )C ₁₂ H ₂₅ E-13 (n) C ₄ H ₉ -O- (n) C ₁₈ H ₃₇ E-14 (n) C ₆ H ₁₃ -O-CH ₂ CH ₂ -O- (n)
C ₆ H ₁₃ E-15 (n) C ₈ H ₁₇ -O-CH ₂ CH ₂ -O- (n)
C ₈ H ₁₇ E-16 (n) C ₁₀ H ₂₁ -O-CH ₂ CH ₂ -O- (n)
C ₁₀ H ₂₁ E-17 (n) C ₁₂ H ₂₅ -O-CH ₂ CH ₂ -O- (n)
C ₁₂ H ₂₅ E-18 (n) C ₁₄ H ₂₉ -O-CH ₂ CH ₂ -O- (n)
C ₁₄ H ₂₉ E-19 CH ₃ -O-CH ₂ CH ₂ -O-(n)C ₈ H ₁₇ E-20 CH ₃ -O-CH ₂ CH ₂ -O-(n)C ₁₂ H ₂₅ E- 21 (n)C ₆ H ₁₃ -O-CH ₂ CH ₂ CH ₂ -O-
(n) C ₆ H ₁₃ E-22 (n) C ₁₀ H ₂₁ -O-CH ₂ CH ₂ CH ₂ -O-
(n) C ₁₀ H ₂₁ E-23 (n) C ₁₂ H ₂₅ -O-CH ₂ CH ₂ CH ₂ -O-
(n) C ₁₂ H ₂₅ Some of the compounds represented by the general formula [] or [] (hereinafter referred to as compounds of the present invention) are commercially available, but they can be easily synthesized according to known methods. For example, the dehydration reaction of aliphatic alcohols, the Williamson synthesis in which aliphatic alcohols, sodium salts of ethylene glycol or propylene glycol, etc. are reacted with alkyl halides, substitution reactions to ethylene glycol dibenzyl ether, etc. , Volume 19, Synthesis of Organic Compounds (edited by the Chemical Society of Japan,
It can be easily synthesized by the synthetic method described in Dai Organic Chemistry, Aliphatic Compounds (Asakura Shoten), 1957, p. 321, etc. The compound of the present invention is contained in a silver halide color photographic light-sensitive material and/or a color developing solution, and is preferably contained in a silver halide color photographic light-sensitive material. When the compound of the present invention is contained in a silver halide color photographic light-sensitive material, this compound is added to any of the photographic constituent layers provided on the support. As used herein, the term "photographic constituent layer" refers to a photosensitive silver halide emulsion layer and non-photosensitive hydrophilic colloid layers such as an intermediate layer, a subbing layer, and a protective layer. When the compound of the present invention is contained in a light-sensitive silver halide emulsion layer, it can be added to one or all of the blue-sensitive layer, green-sensitive layer and red-sensitive layer, but it can be added to the red-sensitive layer forming a cyan dye image. It is preferable to add it to. Further, the photosensitive silver halide emulsion layer may be composed of a plurality of photosensitive silver halide emulsion layers having substantially the same color sensitivity and different photosensitivity. The compound of the present invention can be contained in one or more layers of such a plurality of layers having different photosensitivity. Further, the compound of the present invention may be contained in the non-photosensitive hydrophilic colloid layer, or may be contained in both the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer. A preferred example is when it is contained in a silver halide emulsion layer. As the compounds of the present invention, compounds of the general formula [] or [] can be used alone or in combination. When both are used in combination, the usage ratio is in the range of general formula []: general formula [] = 1; 10 to 10; 1. The compounds of the present invention are generally oil-soluble, and when added to photographic constituent layers, they are generally incorporated in U.S. Pat.
No. 2801171, No. 2272191, and No. 2304940
It is preferable to dissolve it in a high-boiling point organic solvent, if necessary in combination with a low-boiling point solvent, according to the method described in the specification, disperse it, and add it to a hydrophilic colloid solution such as gelatin. as needed,
couplers, hydroquinone derivatives, image stabilizers,
There is no problem in using ultraviolet absorbers etc. At this time, there is no problem in using two or more of the compounds of the present invention in combination. Further, to explain in detail the method of adding the compound of the present invention, one or more of the compounds are added, if necessary, along with couplers, hydroquinone derivatives, image stabilizers, or ultraviolet absorbers, organic acid amides, etc. Carbamates, esters, ketones, hydrocarbons and urea derivatives, in particular dimethyl phthalate, di-n-butyl phthalate, di-octyl phthalate, di-lauryl phthalate, tricresyl phosphate, trioctyl phosphate, High boiling point organic solvents such as di-isooctyl azelate, di-n-butyl sebacate, decalin, N,N-diethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether or fluorine paraffin If necessary, dissolve in a low boiling point organic solvent such as ethyl acetate, butyl acetate, cyclohexanol, cyclohexane or tetrahydrofuran (these high boiling point organic solvents and low boiling point organic solvents can be used alone or in combination). ) Anionic surfactants such as alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids and alkyl succinate sulfonic acids, and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate. Mix with aqueous solution, including high-speed rotation mixer,
It can be emulsified and dispersed using a colloid mill or an ultrasonic dispersion device, and the resulting dispersion can be added to a hydrophilic colloid solution for use. The hydrophilic colloid solution thus obtained (when the hydrophilic colloid solution is a silver halide emulsion, it contains silver halide as described below) is coated by various known methods and exposed to silver halide color photography. Get the materials. When the compound of the present invention is contained in a photosensitive silver halide emulsion layer, the content is 5 to
300% by weight is preferred, particularly 10-150% by weight. The content of the compound of the present invention in the non-photosensitive hydrophilic colloid layer is 0.05 to 2 g, preferably 0.1 g per 1 m ² of the color photographic light-sensitive material.
~1g. When the compound of the present invention is contained in both the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer, the content is 50% by weight or more in the photosensitive silver halide emulsion layer, and the content of the non-photosensitive hydrophilic colloid in the photosensitive silver halide emulsion layer is 50% by weight or more. less than 50% by weight in the layer. The method for processing a silver halide color photographic light-sensitive material according to the present invention basically includes the steps of color development, bleaching, and fixing. In this case, each process may be independent, or two or more of the processes may use processing liquids that have those functions, so that only one process is required. For example, a one-bath bleach-fix solution is an example. In addition, each step can be divided into two or more times as necessary, or a combination of color development, first fixing, and bleach-fixing can be performed. In addition to the above, during the treatment process, if necessary, a pre-hardening bath, a neutralization bath, first development (black and white development),
Various steps such as an image stabilizing bath and water washing are combined. The preferred processing steps used in the present invention are, for example, a series of sequential processing steps, each of which is exemplified below. (1) Color development treatment → bleach-fixing treatment → washing with water (2) color development treatment → bleaching treatment → washing with water → fixing treatment →
Washing with water (3) Color development processing → Stop → Bleaching processing → Washing with water → Fixing processing → Washing with water (4) Black and white development processing → Reverse exposure → Color development processing → Bleach and fixing processing → Washing with water (5) Black and white development processing → Stop → Add capri agent The processing temperature of the method for processing a silver halide color photographic light-sensitive material of the present invention is set within a preferable range depending on the light-sensitive material and the processing recipe. Generally 20-60
℃, but the silver halide color photographic light-sensitive material according to the present invention is particularly suitable for processing at 30℃ or higher. The color developing agent used in the color developing solution includes known color developing agents that are widely used in various color photographic processes. Particularly useful color developing agents are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, -amino-5-(N
-ethyl-N-dodecylamino)-toluene, N
-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxylethylaminoaniline sulfate, 4-amino-3-methyl-N,N-
Diethylaniline hydrochloride, N-ethyl-N-β-
Hydroxylethyl-3-methyl-4-aminoaniline sulfate, 4-amino-N-(β-methoxyethyl)-N-ethyl-3-methylaniline-p
-Toluenesulfonate and the like can be mentioned. These color developing agents may be contained in advance in the silver halide photographic light-sensitive material as the color developing agent itself or as its precursor. The color developing agent precursor is a compound that can produce a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include a Shugar amine reactant precursor and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are described, for example, in U.S. Pat.
No. 3342599, No. 2507114, No. 2695234, No. 3719492, U.S. Patent No. 803783, JP-A No. 1973-
No. 135628, No. 54-79035, and Research Disclosure No. 15159, No. 12146, and No. 13924. In this case, the color developing solution according to the present invention used for color developing processing of silver halide photographic light-sensitive materials containing a color developing agent or its precursor may be a conventionally known alkaline processing solution (so-called an activation bath or an active bath). What is called beta liquid.) is used. These aromatic primary amine color developing agents or their precursors need to be added in an amount that will provide sufficient color development during color development processing. This amount varies depending on the type of silver halide photographic light-sensitive material, but is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of photosensitive silver halide. These color developing agents or their precursors are
They can be used alone or in combination.
In order to incorporate the above compound into a silver halide photographic light-sensitive material, it can be added after being dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc.
It can also be added as an emulsified dispersion using high-boiling organic solvents such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., and latex polymers as described in Research Disclosure No. 14850. It can also be added by being impregnated with. In addition to the aromatic primary amine color developing agent mentioned above, the color developing solution used in the present invention contains alkaline agents such as sodium hydroxide, potassium hydroxide, potassium carbonate, trisodium phosphate, boric acid, acetic acid, etc. of
PH buffer, thioethers, 1-aryl-3-
Known development accelerators such as pyrazolidones, N-methyl-p-aminophenols, and polyalkylene glycol; various organic solvents such as benzyl alcohol, ethanol, butanol, ethylene glycol, diethylene glycol, acetone, and N,N-dimethylformamide; Development inhibitors such as potassium bromide and nitrobenzimidazole, preservatives such as sulfites, hydroxylamine, glucose, alkanols and amines, and water softeners such as polyphosphoric acid compounds and nitrilotriacetic acid are included as necessary. The pH value of the color developer used in the present invention is usually
7.0 or more, preferably about 9.5 to 13.0. The temperature of the color development treatment used in the present invention is 30~
Preferably, the temperature is 40°C and the time is 2 to 5 minutes. Since the silver halide color photographic light-sensitive material of the present invention can obtain good dye images even when processed with a color developer that does not contain benzyl alcohol, there is almost no need to add benzyl alcohol to the color developer, but it is not always necessary to add benzyl alcohol to the color developer. This does not indicate that the alcohol must be removed. When benzyl alcohol is used in the color developer, the dye density can be increased by adding the compound of the present invention, and the amount of coupler used for sensitization and high contrast can be reduced. In the method for processing a silver halide color photographic light-sensitive material of the present invention, the compound of the present invention can also be included in the color developing solution. In this case, the amount of the compound of the present invention to be added depends largely on the solubility of the compound in the color developer, but is 0.01 g to 5.0 g per color developer.
g, preferably 0.02g to 2g, more preferably
It ranges from 0.05g to 1g. Further, the compound of the present invention can also be included in any processing solution prior to processing with a color developer. In the processing method of the present invention, when a bleaching solution is used for the bleaching process, a fixing process is generally performed next using a fixing solution, and when a bleach-fixing solution is used, the bleaching process and the fixing process are performed using the same solution. done at the same time. Bleaching agents used in the bleaching solution or bleach-fixing solution include, for example, red blood salts, dichromates, aminopolycarboxylic acid iron salts, aliphatic polycarboxylic acid metal salts, persulfates, etc. In this case, it is preferable to use a metal complex salt of an organic acid. When a treatment solution containing such a metal complex salt of an organic acid is used, disadvantages such as precipitation of the composition and a decrease in bleaching ability during storage can be effectively prevented. The metal complex salt of an organic acid in the present invention has the effect of oxidizing metallic silver produced during development and converting it into silver halide, and its structure is based on organic acids such as aminopolycarboxylic acid, oxalic acid, citric acid, etc. An acid is coordinated with a metal such as iron, cobalt, or copper. The most preferred organic acid used to form such a metal complex salt of an organic acid is, for example, an aminopolycarboxylic acid represented by the following general formula [] or []. General formula [] HOCO−A ₁ −Z−A ₂ −COOH General formula [] [In each of the above general formulas, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ and A ₆ each represent a divalent hydrocarbon group such as an alkylene group, a cycloalkylene group or an arylene group. Z is a divalent hydrocarbon group such as alkylene group, cycloalkylene group, arylene group, -O- group, -S- group, or N-A ₇ (A ₇ is an alkyl group, cycloalkyl group, aryl group, etc.) represents a monovalent hydrocarbon group or a lower aliphatic carboxylic acid group). ] These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acids represented by the general formula [] or [] include the following. Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, ethyliminodiacetic acid Acetic acid, hydroxyethyliminodiacetic acid, hydroxylmethyliminodiacetic acid, propyliminodiacetic acid, butyliminodiacetic acid, dihydroxyethylglycine ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, ethylenediaminetetraacetic acid Disodium acetate salt, ethylenediaminetetraacetic acid tetra(trimethylammonium) salt, ethylenediaminetetraacetic acid tetrasodium salt, diethylenetriaminepentaacetic acid pentasodium salt, ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid The metal in the sodium salt, propylenediaminetetraacetic acid sodium salt, nitrilotriacetic acid sodium salt, cyclohexanediaminetetraacetic acid sodium salt, and the metal complex salt of an organic acid used in the present invention is a metal that can coordinate with an organic acid, such as Metal complex salts of organic acids such as chromium, manganese, iron, cobalt, nickel, copper, etc., which are particularly preferred in the present invention, are secondary metal salts, such as ferric salts. The metal complex salt of an organic acid in the present invention can be any combination of the above-mentioned organic acid and metal, but particularly preferred are ferric salts of ethylenediaminetetraacetic acid, such as sodium iron() ethylenediaminetetraacetate, ethylenediaminetetraacetic acid Iron () ammonium. Further, metal complex salts of two or more organic acids having different structures may be used in combination. The specific amount used is 0.01 to 0.4 per 1 treatment liquid.
A molar range is preferred. The bleaching solution used in the present invention contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and can also contain various additives. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.
In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, solubilizers such as triethanolamine, aminopolycarboxylic acids or their salts, alkylamines, polyethylene oxides, etc. are used for general bleaching. Anything known to be added to the liquid can be added as appropriate. The bleach-fix solution used in the present invention contains a metal complex salt of an organic acid (for example, an iron complex salt) as a bleaching agent, as well as a silver halide fixing agent such as a thiosulfate, a thiocyanate, or a thiourea. A liquid containing a composition is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to a bleaching agent and the above-mentioned silver halide fixer, or conversely, a composition in which a large amount of a halogen compound such as potassium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide can also be used. As the halogen compound, in addition to potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. can be used. The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as those used in normal fixing processing.
For example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Typical examples include thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. The bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide,
PH buffering agents consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, organic chelating agents such as aminopolycarboxylic acids, solubilizing agents such as alkanolamines, and organic amines. Stain inhibitors such as
Methanol, N,N-dimethylformamide,
An organic solvent such as N,N-dimethylsulfoxide is appropriately contained. Further, when performing automatic development processing, the bleach solution or bleach-fix solution is usually replenished with a replenisher by an automatic replenishment system. That is, it supplements the components in the bleach solution or bleach-fix solution that are consumed depending on the amount of processing of silver halide photographic light-sensitive materials, supplements the dilution caused by the solution brought in from color development processing or water washing processing, or supplements the bleach solution. Alternatively, the necessary components are replenished from the bleach-fix solution to compensate for those carried out by the processed silver halide photographic material.
Therefore, the replenisher is usually more concentrated than the bleach or bleach-fix solution, and the degree of concentration is appropriately selected depending on the amount of components to be replenished or the amount of the bleach or bleach-fix solution. be done. The processing time of the bleaching step and bleach-fixing step according to the present invention is preferably 0.5 to 2 minutes, more preferably 1 to 1.5 minutes. The processing temperature is usually 25 to 40°C. In the present invention, the water washing step usually takes about 25 to 35 hours.
The process is carried out for about 2 to 4 minutes using water at
It is about 100 to 300c.c. per ^200cm2 . In recent years, in order to reduce the amount of water used in this washing process, methods such as a multi-stage countercurrent washing method have been used, and this method is described in, for example, Japanese Patent Application Laid-Open Nos. 57-8543 and 56.
-Described in No. 146135, etc. In the photographic emulsion layer of the silver halide color photographic light-sensitive material of the present invention, aromatic primary
Contains a dye-forming coupler that can form cyan, magenta, and yellow dyes through a coupling reaction with an oxidized product of a grade amine color developing agent. Among these dye-forming couplers, yellow dye-forming couplers are of the benzoylacetanilide type, pivaloylacetanilide type, or those in which the carbon atom at the coupling position has a substituent that can be separated during the coupling reaction (a so-called split-off group). It is a substituted 2-equivalent type yellow dye-forming coupler, and the magenta dye-forming coupler is a 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indazolone type, or a 2-equivalent magenta dye having a split-off group. The cyan dye-forming coupler is a phenol-based, naphthol-based, or 2-equivalent cyan dye-forming coupler having a split-off group. Among such dye-forming couplers, yellow dye-forming couplers are disclosed in, for example, U.S. Pat.
Same No. 2908513, Same No. 3227155, Same No. 3227550,
Same No. 3253924, Same No. 3265506, Same No. 3277155,
Same No. 3341331, Same No. 3369895, Same No. 3384657,
Same No. 3408194, Same No. 3415652, Same No. 3447928,
Same No. 3551155, Same No. 3582322, Same No. 3725072,
German Patent No. 1547868, German Patent No. 2057941, German Patent No.
No. 2162899, No. 2163812, No. 2213461, No. 2219917, No. 2261361, No. 2263875,
Special Publication No. 49-13576, Japanese Patent Publication No. 48-29432, No. 48
-66834, 49-10736, 49-122335, 49-122335, 49-10736, 49-122335,
No. 50-28834, No. 50-132926, No. 55-144240,
It is described in each specification of No. 56-87041. Regarding magenta dye-forming couplers,
For example, US Pat. No. 2,600,788, US Pat. No. 3,061,432,
Same No. 3062653, Same No. 3127269, Same No. 3311476,
Same No. 3152896, Same No. 3419391, Same No. 3519429,
Same No. 3558318, Same No. 3684514, Same No. 3705896,
Same No. 3888680, Same No. 3907571, Same No. 3928044,
Same No. 3930861, Same No. 3930816, Same No. 3933500,
JP-A-49-29639, JP-A No. 49-111631, JP-A No. 49-
No. 129538, No. 51-112341, No. 52-58922, No.
No. 55-62454, No. 55-118034, No. 56-38643,
No. 56-135841, Special Publication No. 46-60479, No. 52-
No. 34937, No. 55-29421, No. 55-35696, US Pat. No. 1,247,493, Belgian Patent No. 792,525, and West German Patent No. 2,156,111. Additionally, for cyan dye-forming couplers,
For example, US Patent No. 2369929, US Patent No. 2423730,
Same No. 2434272, Same No. 2474293, Same No. 2698794,
Same No. 2706684, Same No. 2772162, Same No. 2801171,
Same No. 2895826, Same No. 2908573, Same No. 3034892,
Same No. 3046129, Same No. 3227550, Same No. 3253294,
Same No. 3311476, Same No. 3386301, Same No. 3419390,
Same No. 3458315, Same No. 3476563, Same No. 3516831,
Same No. 3560212, Same No. 3582322, Same No. 3583971,
Same No. 3591383, Same No. 3619196, Same No. 3632347,
Same No. 3652286, Same No. 3737326, Same No. 3758308,
No. 3779768, No. 3839044, West German Patent No.
No. 2163811, No. 2207468, Special Publication No. 39-27563,
45-28836, JP-A No. 47-37425, 50-
No. 10135, No. 50-25228, No. 50-112038, No. 50
−117422, No. 50-130441, No. 53-109630,
No. 55-32071, No. 55-163537, No. 56-1938,
No. 56-13643, No. 56-29235, No. 56-65134,
No. 56-104333, Research Disclosure No. 1976, 14853, etc. Next, specific representative examples of each dye-forming coupler used in the present invention are shown below, but the present invention is not limited thereto. (Y-1) α-(4-carboxyphenoxy)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide. (Y-2) α-benzoyl-2-chloro-5-[γ-(2,
4-di-t-amylphenoxy)butyramide]
Acetanilide. (Y-3) α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide. (Y-4) α-(4-Carboxyphenoxy)-α-pivalyl-2-chloro-5-[α-(3-pentadecylphenoxy)butyramide]acetanilide. (Y-5) α-(1-benzyl-2,4-dioxo-3-
imidazolidinyl)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide. (Y-6) α-[4-(1-benzyl-2-phenyl-3,
5-dioxo-1,2,4-triazolidinyl)]
-α-pivalyl-2-chloro-5-[γ-(2,4
-di-t-amylphenoxy)butyramide]acetanilide. (Y-7) α-acetoxy-α-{3-[α-(2,4-di-t-amylphenoxy)butyramide]benzoyl}-2-methoxyacetanilide. (Y-8) α-{3-[α-(2,4-di-t-amylphenoxy)butyramide]benzoyl}-2-methoxyacetanilide. (Y-9) α-[4-(4-benzyloxyphenylsulfonyl)phenoxy]-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide. (Y-10) α-pivalyl-α-(4,5-dichloro-3-
(2H)-pyridazol-2-yl)-2-chloro-5-
[(hexadecyloxycarbonyl)methoxycarbonyl]acetanilide. (Y-11) α-pivalyl-α-[4-(p-chlorophenyl)-5-oxo-Δ ² -tetrazolin-1-yl]-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl ] Acetanilide. (Y-12) α-(2,4-dioxo-5,5-dimethyloxazolidin-3-yl)-α-pivalyl-2-
Chloro-5-[α-(2,4-di-t-amylphenoxy)butyramide]acetanilide. (Y-13) α-pivalyl-α-[4-(1-methyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-2-chloro-5-[γ-(2 ,4-
di-t-amylphenoxy)butyramide]acetanilide. (Y-14) α-pivalyl-α-[4-(p-ethylphenyl)-5-oxo-Δ ² -tetrazolyl-1-yl]-2-chloro-5-[γ-(2,4-di- t-
amylphenoxy)butyramide]acetanilide. (Y-15) α-(1-benzyl-2-phenyl-3,5-
Dioxo-1,2,4-triazolidinyl)-α
-pivalyl-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide. (M-1) 1-(2,4,6-trichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone. (M-2) 1-(2,4,6-trichlorophenyl)-3-
(3-dodecylsuccinimidobenzamide)-5
-Pyrazolone. (M-3) 4,4'-methylenebis{1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t
-amylphenoxyacetamide)benzamide]-5-pyrazolone}. (M-4) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone. (M-5) 1-(2-chloro-4,6-dimethylphenyl)
-3-{3-[α-(3-pentadecylphenoxy)
butylamide]benzamide}-5-pyrazolone. (M-6) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecylcarbamoylanilino)-5-pyrazolone. (M-7) 3-ethoxy-1-{4-[α-(3-pentadecylphenoxy)butyramide]phenyl}-5
-Pyrazolone. (M-8) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-tetradecanamide anilino)
-5-pyrazolone. (M-9) 1-(2,4,6-trichlorophenyl)-3-
{2-chloro-5-[α-(3-t-butyl-4-
hydroxyphenoxy)tetradecanamide]anilino}-5-pyrazolone. (M-10) 1-(2,4,6-trichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-4-acetoxy-5-
Pyrazolone. (M-11) 1-(2,4,6-trichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-4-ethoxycarbonyloxy-5-pyrazolone. (M-12) 1-(2,4,6-trichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamido)benzamide]-4-(4-chlorocinnamoyloxy)-5-pyrazolone. (M-13) 4,4'-benzylidene bis [(1-2,4,6
-trichlorophenyl)-3-{2-chloro-5-
[γ-(2,4-di-t-amylphenoxy)butyramide]anilino}-5-pyrazolone. (M-14) 4,4'-benzylidene bis[1-(2,3,4,
5,6-pentachlorophenyl)-3-{2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]anilino}-5-pyrazolone]. (M-15) 4,4'-(2-chloro)benzylidene bis[1
-(2,4,6-trichlorophenyl)-3-(2
-Chloro-5-dodecylsuccinimideanilino-
5-pyrazolone]. (M-16) 4,4'-methylenebis[1-(2,4,6-trichlorophenyl)-3-{3-[α-(2,4-di-t-amylphenoxy)butyramide]benzamide} -5-pyrazolone. (M-17) 1-(2,6-dichloro-4-methoxyphenyl)-3-(2-methyl-5-acetamidoanilino)-5-pyrazolone. (M-18) 1-(2-chloro-4,6-dimethylphenyl)
-3-(2-methyl-5-chloroanilino)-5-
Pyrazolone. (M-19) 1-(2,4,6-trichlorophenyl)-3-
(4-nitroanilino)-5-pyrazolone. (M-20) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecenylsucciimido-anilino)-5-pyrazolone. (M-21) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-tridecanamido-anilino)-5
-Pyrazolone. (M-22) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-tetradecanamide)anilino-4-(2-dodecylamide)phenylthio-
5-Pyrazolone. (M-23) 1-(2,4,6-trichlorophenyl)-3-
[2-chloro-5-(2,4-di-t-amylphenoxy)acetamide]anilino-4-phenylthio-5-pyrazolone. (M-24) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-tetradecanamide)anilino-4-(2-methoxy)phenylthio-5-pyrazolone. (M-25) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-tetradecanamide)anilino-4-benzylthio-5-pyrazolone. (C-1) 1-hydroxy-N-[δ-(2,4-di-t-
amylphenoxy)butyl]-2-naphthamide. (C-2) 2,4-dichloro-3-methyl-6-(2,4
-di-t-amylphenoxyacetamido)phenol. (C-3) 2,4-dichloro-3-methyl-6-[α-
(2,4-di-t-amylphenoxy)butyramide]phenol. (C-4) 1-Hydroxy-4-(3-nitrophenylsulfonamide)-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide. (C-5) 1-hydroxy-4-[(β-methoxyethyl)
Carbamoyl]methoxy-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide. (C-6) 1-Hydroxy-4-(isopropylcarbamoyl)methoxy-N-dodecyl-2-naphthamide. (C-7) 2-perfluorobutyramide-5-[α-
(2,4-di-t-amylphenoxy)hexanamide]phenol. (C-8) 1-hydroxy-4-(4-nitrophenylcarbamoyl)oxy-N-[δ-(2,4-di-t
-amylphenoxy)butyl]-2-naphthamide. (C-9) 2-(α,α,β,β-tetrafluoropropionamide-5-[α-(2,4-di-t-amylphenoxy)butyramide]phenol. (C-10) 1-hydroxy- N-dodecyl-2-naphthamide. (C-11) 1-hydroxy-(4-nitro)phenoxy-
N-[δ-(2,4-di-t-amylphenoxy)
butyl]-2-naphthamide. (C-12) 1-hydroxy-4-(1-phenyl-5-tetrazolyloxy)-N-[δ-(2,4-di-t
-amylphenoxy)butyl]-2-naphthamide. (C-13) 2-(α,α,β,β-tetrafluoropropionamide)-4-β-chloroethoxy-5-[α
-(2,4-di-t-amylphenoxy)butyramide]phenol. (C-14) 2-chloro-3-methyl-4-ethylcarbamoylmethoxy-6-[α-(2,4-di-t-amylphenoxy)butyramide]phenol. (C-15) 2-benzoylamino-4-chloro-5-[α
-(4-butanesulfonaminophenoxy)-α-
Dodecyl-acetylamino]phenol. (C-16) 2-(4-cyanobenzoyl)amino-4-chloro-5-[α-(2-dodecylsulfonamino)
-α-dimethyl-acetylamino]phenol. (C-17) 2-(perfluorobenzoyl)amino-4-
Chloro-5-[α-(3-dodecylsulfonamino)-α-butyl-acetylamino]phenol. (C-18) 2-(perfluorobenzoyl)amino-4-
Chloro-5-[(2,4-di-t-butylphenoxy)acetylamino]phenol. (C-19) 2-Benzoylanilino-4-chloro-5-
[(4-dodecyloxy)phenoxybutanamide] phenol. When the compound of the present invention is added to a silver halide color photographic light-sensitive material using a high boiling point organic solvent,
Preferred high boiling point organic solvents have a boiling point of about 170
It is an organic solvent that is immiscible with water at temperatures above etc.), phosphate esters (diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, dioctyl butyl phosphate, trihexyl phosphate, trioctyl phosphate, etc.),
Citric acid esters (acetyl tributyl citrate, tributyl citrate, etc.), benzoic acid esters (butyl benzoate, octyl benzoate, etc.), alkylamides (diethyl laurylamide, etc.), sebacic acid esters (diethylhexyl sebacate, etc.),
Stearic acid esters (butyl stearate, etc.),
Maleic acid esters (dinonyl maleate, etc.),
Examples include succinate esters (diethyl succinate, etc.), adipate esters (dioctyl adipate, etc.), pyrrolidone (N-dodecylpyrrolidone, etc.), and the like. Examples of low boiling point (approximately 30 to 150°C) organic solvents used as auxiliary solvents together with such high boiling point organic solvents include lower acetyl acetate (ethyl acetate, butyl acetate, β-ethoxyethyl acetate, etc.), butyl alcohol, Methyl isobutyl ketone, chloroform, hexane, cyclohexane,
Examples include ethylene glycol, acetone, ethanol, dioxane, dimethylformamide and the like. When the compound of the present invention is contained in a silver halide color photographic light-sensitive material, it is preferably contained in a high-boiling organic solvent together with a photographic coupler as described above. Furthermore, the effect of the present invention is further enhanced if the photographic coupler is the cyan dye-forming coupler. The silver halide contained in the silver halide emulsion layer of the present invention is any one of silver iodobromide, silver chlorobromide, silver bromide, silver chloroiodobromide, silver chloride, and silver chloroiodide. It may be. These silver halides may be produced by any of the ammonia method, neutral method, acidic method, etc., and may be produced by any of the simultaneous mixing method, forward mixing method, reverse mixing method, convergence method, etc. Furthermore, silver halide grains with or without boundaries between different halogen compositions can be effectively used in the present invention. The binder used in the photographic constituent layer of the silver halide color photographic light-sensitive material according to the present invention includes:
Gelatin such as alkali-processed gelatin or acid-processed gelatin is the most common, but some of this gelatin and derivative gelatin such as phthalated gelatin, phenylcarbamoyl gelatin, albumin, agar, gum arabic, alginic acid, partially hydrolyzed gelatin, etc. Cellulose derivative, partially hydrolyzed polyvinyl acetate,
Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used in combination. The silver halide emulsion used in the present invention is a salt of a noble metal such as ruthenium, rhodium, palladium, iridium, platinum, or gold (for example, ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadite, potassium chloroaurate, etc.). ), active gelatin, sulfur sensitization with unstable sulfur compounds (e.g., sodium thiosulfate, etc.), selenium sensitization with selenium compounds, or stannous salts, polyamines, etc.
Chemical sensitization such as reduction sensitization under pAg conditions can be performed. Further, these silver halide emulsions can be optically sensitized using various sensitizers in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes that can be used at this time include, for example, US Pat.
No. 2739149, No. 2213995, No. 2213995, No. 2739149, No. 2213995, No.
Cyanine dyes, merocyanine dyes, or complex cyanine dyes described in the specifications of No. 2493748 and No. 2519001, West German Patent No. 929080, and U.S. Patent No. 505979 are used alone or in combination of two or more. be able to. These various optical sensitizers are used for purposes other than their original purpose, such as preventing fog, preventing deterioration of photographic performance during storage of silver halide color photographic materials, and controlling development (for example, gradation). It can also be used for purposes such as control, etc. The photographic constituent layers of the silver halide color photographic light-sensitive material according to the present invention may further contain chemical sensitizers such as thioether compounds, quaternary ammonium salt compounds, or polyalkylene oxide compounds, triazoles, imidazoles, etc. , azaindenes,
Stabilizers such as benzothiazolium compounds, zinc compounds, cadmium compounds, and mercabutanes can be used within the range that does not impair the effects of the present invention. Further, the photographic constituent layers of the silver halide color photographic light-sensitive material according to the present invention may contain various photographic additives, such as ultraviolet absorbers (for example, benzophenone compounds and benzotriazole compounds), development accelerators (for example, 1 -aryl-3-pyrazolidone compounds), surfactants (e.g., sodium alkylnaphthalenesulfonates, sodium alkylbenzenesulfonates, sodium alkylsuccinate sulfonates, and polyalkylene compounds), water-soluble anti-irradiation dyes (e.g., azo compounds, styryl compounds, oxonol compounds, anthraquinone compounds, triphenylmethane compounds, etc.), hardeners (e.g., halogen-substituted S-triazine compounds, activated vinyl compounds, ethyleneimino compounds, epoxy (e.g., glycerin, polyalkylene glycols, aqueous polymer dispersions (latex, etc.), solid or liquid paraffin, etc.) can be added. Supports used in the silver halide color photographic light-sensitive material according to the present invention include supports such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, and polystyrene; and polypropylene, etc.), etc.), etc.)
It can be used as appropriate depending on the purpose. This support can generally be subjected to various surface improvement treatments in order to improve its adhesion to silver halide emulsions. For example, it is also possible to use a material whose surface has been roughened mechanically or with an organic solvent, which has been subjected to surface treatment such as electron impact treatment or fire treatment, or which has been subjected to subbing treatment such as providing a subbing layer. To coat each constituent layer of the silver halide color photographic light-sensitive material onto this support, commonly known coating methods such as dipping coating, roller coating,
It is applied by a method such as pea coating or curtain flow coating, and then dried. Specific Examples of the Invention Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 The following layers were sequentially coated from the support side onto a paper support coated with polyethylene to prepare six types of silver halide color photographic light-sensitive materials (comparative samples 1A to 6A).
I made it. In addition, the amount added is shown in the amount (g) per 1 m ² in all the following examples unless otherwise specified. Layer 1...2.1 g of gelatin, 0.35 g (in terms of silver) of blue-sensitive silver chlorobromide emulsion (silver bromide 85 mol%, average grain size 0.65 μm), and 1.2×
Contains 0.3 g of dioctyl phthalate (hereinafter referred to as DOP) in which 10 ^-3 moles of the yellow coupler shown in Table 1 and 0.015 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as HQ-1) are dissolved. The layer that does. Layer 2: Gelatin protective layer containing 1.3g gelatin and 0.05g bisvinylsulfonyl methyl ether. On the other hand, in the comparative samples (1A to 6A), the silver halide color photographic light-sensitive materials of the present invention were the same as the comparative samples except that layer 1 contained 0.4 g of the exemplary compound (E-3) of the present invention ( Sample 1B of the present invention
~6B) was created. Incidentally, this exemplified compound E-3 was dispersed in gelatin at the same time as the above-mentioned yellow coupler. Six kinds of comparative samples (1A
~6A) and six types of samples of the present invention (1B~6B) were exposed through an optical wedge and then processed in the following steps. The color developer (A) is a normal color developer containing benzyl alcohol and ethylene glycol for dissolving it, and the color developer (B)
does not contain benzyl alcohol and ethylene glycol. Processing process Temperature Time Color development 33°C 3 minutes 30 seconds Bleach-fixing 33°C 1 minute 30 seconds Washing 30-34°C 3 minutes Drying 60-80°C 2 minutes Also used color developing solutions (A) and (B), The composition of the bleach-fix solution is as follows. Color developer (A)

[Table] 〓Adjust.
Color developer (B) Color developer (A) from which ethylene glycol and benzyl alcohol have been removed. bleach-fix solution

[Table] 〓ru.
The reflection density of the obtained sample was measured using blue monochromatic light, and the results shown in Table 1 were obtained from the characteristic curve. In the table, γ is the gradation of reflection density 0.5 to 1.5, and relative sensitivity is the comparison samples (1A to 6A) that do not contain Exemplary Compound E-3 of the present invention treated with color developer A containing benzyl alcohol. The relative sensitivity is shown when the sensitivity is set to 100 for each case.

[Table] From the results shown in Table-1, samples 1B to 6B of the present invention
When processed with a color developing solution (A) containing benzyl alcohol, good results were obtained in terms of high contrast, sensitization, and maximum density, and
It can be seen that even when processed with a color developing solution (B) containing no benzyl alcohol, good photographic properties are exhibited. Example 2 In the same manner as in Example 1, the following two layers were coated on a polyethylene-coated paper support to prepare a silver halide color photographic material. (Comparative sample 7) Layer 1...2.1 g of gelatin, 0.28 g of red-sensitive silver chlorobromide emulsion (silver bromide composition 65 mol%, average grain size 0.35 μm), and 0.42 g of cyan coupler C-15 and a layer containing 0.12 g of DOP dissolved in 0.005 g of HQ-1. Layer 2: Gelatin protective layer containing 1.3g gelatin and 0.05g bisvinylsulfonyl methyl ether. Further, Samples 8 to 16 were prepared in the same manner as Comparative Sample 7 except that 0.28 g of the compound shown in Table 2 was contained in Layer 1. The ten kinds of samples 7 to 16 obtained were treated in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[Table] From the results shown in Table 2, samples 11 to 16 of the present invention
When processed with a color developer (A) containing benzyl alcohol, good results were obtained in both high contrast and maximum density, and when processed with a color developer (B) that did not contain benzyl alcohol. It can be seen that good gradation and maximum density characteristics can be obtained even when Example 3 After corona discharge was applied to a paper support coated on both sides with polyethylene, the following seven layers were sequentially applied from the support side to prepare a multilayer color photographic paper.
(Comparative sample 17) Layer 1...1.5g gelatin, 0.33g (in terms of silver) blue-sensitive silver chlorobromide emulsion (silver bromide 85 mol%, average grain size 0.65 μm), 0.6 × 10 ^-3 mol yellow coupler (Y-5) and 0.9×
10 ⁻³ moles of yellow coupler (Y-15)
and 0.25 in which 0.015g of HQ-1 was dissolved.
A layer containing g DOP. Layer 2...0.9g gelatin and 0.09g HQ-1
A layer containing 0.06g of DOP dissolved in Layer 3...1.3 g of gelatin, 0.27 g (in terms of silver) of green-sensitive silver chlorobromide emulsion (silver bromide 70 mol%, average grain size 0.48 μm), 0.59 x 10 ^-3 mol of magenta coupler (M −4) and 0.015
A layer containing DOP in which g of HQ-1 was dissolved. Layer 4...1.5g gelatin, 0.8g UV absorber UV-1 shown below and 0.04g HQ-1
A layer containing 0.6g of DOP dissolved in Layer 5...1.3 g of gelatin, 0.3 g (in terms of silver) of red-sensitive silver chlorobromide (silver bromide 65 mol%, average particle size 0.35 μm), 0.75×10 ^-3 mol of cyan coupler (C- 3) and 0.005g of HQ-1
A layer containing 0.2g of DOP dissolved in Layer 6...1.0g gelatin, 0.2g ultraviolet absorber
UV-1 and 0.01g of HQ-1 were dissolved.
Layer containing 0.015g of DOP. Layer 7: A layer containing 1.0 g of gelatin and 0.015 g of polyvinylpyrrolidone. Furthermore, Sample 18 was prepared in the same manner as Comparative Sample 16, except that in Comparative Sample 17, 50% by weight of the exemplary compound E-23 of the present invention was added to the coupler dispersion in Layer 5, and Layer 1 Sample 19 was prepared in the same manner as Comparative Sample 17 except that 70% by weight of the exemplified compound E-5 of the present invention was added to the coupler dispersion of layer 5 based on the coupler. The obtained samples 17 to 19 were exposed to white light wedge and then treated with color developing solutions (A) and (B) in the same manner as in Example 1, respectively. The results obtained are shown in Table 3. In the table, B, G, and R indicate the results of density measurements using blue, green, and red monochromatic lights, respectively.

[Table] From the results shown in Table 3, color photographic paper samples 18 and 19 of the present invention have good gradation and maximum density even when processed with color developer (B) that does not contain benzyl alcohol. I know what you're doing. Example 4 Three types of color photographic paper, Samples 17, 18 and 19 used in Example 3, were exposed to a fluorescent lamp for 2 seconds and then subjected to color development treatment with the color developer (A) for 3 minutes and 30 seconds. Processed with fatigue bleach-fix solution at 33℃ for 1 minute and 30 seconds,
Then, it was washed with water and dried. The maximum red color density of the obtained samples 17', 18' and 19' was measured and the results are shown in Table 4. Fatigue bleach-fix solution 10% per bleach-fix solution used in Example 1
Add 20ml of silver nitrate aqueous solution and reduce the redox potential to -
Adjusted to 100mV (reference electrode: silver-silver chloride electrode).

[Table] From the results shown in Table 4, samples 18' and 19' of the present invention maintain a good maximum red density without producing much anleuco dye even when processed with fatigue bleach-fix solution. I know that there is.

Claims (1)

[Scope of Claims] 1. A halogen-based silver halide color photographic light-sensitive material which is imagewise exposed and then subjected to color development treatment in the presence of at least one of the compounds represented by the following general formulas [] and []. Processing method for silver chemical color photographic materials. General formula [] R ₁ -O-R ₂ General formula [] R ₃ -O(-CH ₂ )- _o -O-R ₄ (wherein, R ₁ and R ₂ are each an alkyl group without a substituent , and the total number of carbon atoms of R ₁ and R ₂ is 8 to 32. Also, R ₃ and R ₄ are
Each represents an alkyl group having no substituent or substituted with phenyl, and the total number of carbon atoms of R ₃ and R ₄ is 9 to 32. n represents 2 or 3. )