JPS60172042A - Process for treating color photographic sensitive material comprising silver halide - Google Patents

Abstract

PURPOSE:To improve color developing effect of a coupler, to reduce remaining amt. of dead coupler, and to obtain high density of dye by subjecting a color photographic sensitive material comprising silver halide to image exposure, then to color developing treatment in the presence of at least one specified compd. CONSTITUTION:The specified compd. is expressed by the formula I or II wherein R1 and R2 is each an alkyl group; R3 and R4 is each an alkyl group, and n is 2 or 3. I and II are contained in a color photographic sensitive material comprising silver halide and/or in a color developing liquid. When it is to be contained in a photosensitive material, it is incorporated in the photosensitive silver halide emulsion layer, and non-photosensitive hydrophilic colloid layer such as intermediate layer, undercoating layer, or protecting layer. The compds. I and/or IImay be used alone or in combination. They are used in the form of a mixture with aq. soln. contg. a surface active agent, or by adding a liquid dispersion thereof to a hydrophilic colloid soln. Suitable content of the compd. to be incorporated in the photosensitive emulsion layer is 5-300wt% basing on the weight of coupler, and suitable content of the compd. to be incorporated in the non-photosensitive hydrophilic colloid layer is 0.05-2g per 1m<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background Technical 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 development of couplers is improved.

Prior Art and Its Problems Usually, silver halide color photographic materials are developed 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 carried out. 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 produce cyan dye, magenta dye, etc. Forms a color photographic image consisting of dye and yellow dye.

In this method, a so-called internal color development method is widely used in which a silver halide emulsion layer is previously included with turntable.

The cyan, magenta, and yellow couplers used in this internal color development method are blue, magenta, and yellow couplers used to prevent color mixing of dyes.
It is necessary to fix each coupler in a silver halide emulsion layer that is selectively sensitive to green and red light, and for this reason, these couplers have long-chain aliphatic groups in their molecules as diffusion-preventing groups. . 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 these, benzyl alcohol is widely used as such a penetrant, and when processed with a color developing solution containing it, good coupler color development can be obtained, as well as improvements in sensitivity, gradation, maximum density, etc. Color photographic images with good photographic performance can be obtained.

However, even when this benzyl alcohol is used, it is rare that the coupler used undergoes a complete color reaction in the highest concentration range, and in most cases, some couplers react by oxidation of a sufficient amount of color developing agent. Even if a body exists, it does not contribute to color development and remains as a so-called dead coupler.

Therefore, in order to obtain sufficient dye density, it is necessary to use more coupler than necessary, which increases production costs and increases the amount of gelatin used when producing color photographic materials. This may make high-speed coating difficult, or may cause problems such as discoloration of uncolored areas of color photographic materials after processing due to heat, humidity, and light. There is.

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, Japanese Patent Application Laid-open Nos. 58-42045 and 58-95346 disclose novel couplers having 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, dead couplers that contain benzyl alcohol In order to develop a color photographic light-sensitive material with a color developer and obtain good color development, the color developer 1 should contain 10 to 15 or more benzyl alcohol. However, since benzyl alcohol has low solubility in water, benzyl alcohol is usually prepared by adding a considerable amount of polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin, and triethanolamine as an auxiliary solvent. It was necessary to solubilize.

By the way, such benzyl alcohol and polyhydric alcohols have low BOD (biochemical oxygen demand) and COD.
(Chemical Oxygen Demand) etc. are high, so from the perspective of environmental pollution, it is desirable to reduce the amount by 9 or not use it at all.In particular, it is desirable to reduce benzyl alcohol to 8 or less per 1 part of the color developer. If it is possible to do so, it is possible to avoid the use of polyhydric alcohol as a co-solvent, and furthermore, it has the secondary advantage of being able to reduce the pollution load.

For this reason, we use as little benzyl alcohol as possible.
Alternatively, it is desired to develop a photographic processing method or a silver halide color photographic material in which silver halide color photographic light-sensitive materials are color-developed using a color developing solution that does not contain any color developer, and the color development properties of couplers are not impaired. research is being conducted. For example, Japanese Patent Application Laid-Open No. 58-50536 proposes processing a photosensitive material containing 1-aryl-3-pyrazolidone by adding benzyl alcohol to a color developing solution 1 to 8. . however,
The technology described in this publication cannot improve color development, and it does not improve dye density for a given amount of developed silver, and this drawback is especially true in the mid-density region of the characteristic curve. big.

■ 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 dead coupler remaining, and use the minimum amount of coupler necessary. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material, which allows a high dye density to be obtained in a small amount.

A second object of the present invention is to provide silver halide with high dye density and good gradation even when processed with a color developer containing no benzyl alcohol or only a small amount of benzyl alcohol. An object of the present invention is to provide a method for processing color photographic materials.

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.

■Specific structure of the invention The above-mentioned object of the present invention is to perform color development in the presence of at least one of the compounds represented by the following general formulas [■] and (n) after imagewise exposure of a silver halide color photographic light-sensitive material. This is achieved by a method for processing a silver halide color photographic material, which is characterized by processing.

General formula [■] R1-0-R2 General formula (II) R3-0+ CH2+1i-0-R4 (wherein, R1 and R2 represent an alkyl group, and bird and R4 each represent an alkyl group, n teeth,
2 or 3t-represented. ) In the above general formula CI), R, and R2 are each preferably a linear or branched alkyl group having 1 to 20 carbon atoms, which may be the same or different, such as a methyl group, an ethyl group, an n- Propyl group, 1so-propyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-
These include hexyl group, n-decyl group, n-dodecyl group, n-heptadecyl group, n-octadecyl group, and the like. Further, the total number of carbon atoms in the alkyl groups represented by R□ and R2 is preferably 8 to 32.

R3 and R4 in the above general formula CII) each preferably represent a straight chain or branched alkyl group which may be the same or different, more preferably having 1 to 20 carbon atoms.
For example, methyl group, ethyl group, n-propyl group, n-
Butyl group, n-hexyl group, n-octyl group, 2-ethyl-hexyl group, n-decyl group, n-dodecyl group, n-
Such as octadecyl group. 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 (e.g., methyl group, ethyl group, 18o-propyl group, t- butyl group, etc.), alkoxy groups having 1 to 4 carbon atoms (e.g.,
methoxy group, ethoxy group, etc.),
The total number of carbon atoms in the alkyl groups represented by R3 and R4 is preferably 9 to 32. Here, R3% R4
When the alkyl group of is substituted with a phenyl group, R3
, R4 is preferably a methyl group or an ethyl group.

Specific examples of the compounds represented by the general formula CI) or the formula used in the present invention are shown below, but the present invention is not limited to these compounds.

Exemplary compound E-1po6H110-■C,H□1 E-2 ■C6H13-0-鵠, H13E 3 (n)
C,,Hl,0 (n)CgH17E -5鵠1゜R2
,→-(n)01oH2□E 6 (n)C12H26
0-(tl)CI2R25E-7fn)C□, R29-
0→C14H2゜E -8(n)C,,H,C on one machine,
, H E -9CH-0-(n)C14H.

E 10 (tlc4He O-@CtoHz, E-1
1 (b) C4H, -〇- (f) C8H17E -12 (
n) C4H, -0-(n) C1□H2゜E 13 (n
lc4H,0(n)C18H,.

E -14(n)C,R13-0-OH2CH,-0-
(nlc6H13E -15(nlc, H,, -0-C
H, CH, -0-(n)C8H,7E -16(n)C
,,)H21-o-CH2C)f2-0-(n)CIo
H2゜E-17■C1□H2!1-O-CH2CH2-
0-(to)C1□HahE-18(company)C,4H2g-0
-CH2CH2-0- ■C14H29 -19CH-0
-CH2CH2-0-■C3H1□E-20CH3-0
-CH2CH2-0-■C1□H25E -21(n)
C6H, 3-O-CH2CH2CH2-0-(n)C,
H13E-22WCl(, H21-0-CH2CH2
CH, -0-(n)C1(, H21E-23■C1□H
A-0-CH2CH2CH2-0-(c)C1□H3K
-29<I>CH, -0-CH, CH2-0-11n
lc8H, 7E -ao C2H, -0-CH2CH2
-0-cH20 Although some of the compounds represented by the general formula mt or (II) (hereinafter referred to as compounds of the present invention) are commercially available, they can be easily synthesized according to known methods. I can do it. For example, dehydration of aliphatic alcohols, 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. Experimental chemistry Lectures, Volume 19, Synthesis of Organic Compounds I (edited by the Chemical Society of Japan,
Maruzen Co., Ltd.), 1957, p. 176 and Dai Organic Chemistry ■, Aliphatic Compounds ■ (Breakfast Shoten), 1957, 32
It can be easily synthesized by the synthesis method described on page 1.

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 film-protecting 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 back-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. good. A preferred example is when it is contained in a silver halide emulsion layer.

As the compounds of the present invention, compounds of general formula CI) or (IF) can be used alone or in combination. When using both in combination, the usage ratio is the general formula [■] Koni set (If) = 1:10-1
The range is 0:1.

The compounds of the present invention are generally oil-soluble, and when added to photographic constituent layers, they are generally used in U.S. Pat.
No. 22,027, No. 2,801,170, No. 2.
No. 801,171, No. 2,272,191, and No. 2,304,940, it is dissolved in a high boiling point organic solvent, if necessary, in combination with a low boiling point solvent. It is preferable to disperse it and add it to a hydrophilic colloid solution such as gelatin. At this time, if necessary, couplers, hydroquinone derivatives, image stabilizers, ultraviolet absorbers, etc. may be used in combination. 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, 1
The species or two or more of the compounds are optionally combined with a coupler,
Along with hydroquinone derivatives, image stabilizers or ultraviolet absorbers, organic acid amides, carbamates, esters, ketones, hydrocarbons and urea derivatives, especially dimethyl phthalate, di-n-butyl phthalate, di-octyl Phthalate, di-lauryl phthalate, tricresyl phosphate, trioctyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, decalin, N,N-diethyl-caprylamidobutyl, N,N-diethyl laurylamide, n - If necessary, add ethyl acetate, butyl acetate,
Dissolved in a low boiling point organic medium such as cyclohesanol, cyclohexane or tetrahydrofuran (these high boiling point organic solvents and low boiling point organic solvents may be used alone or in combination), an alkylbenzenesulfonic acid,
Mixing with an aqueous solution containing an anionic surfactant such as alkylnaphthalene sulfonic acid and alkyl succinate sulfonic acid and/or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate; 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.

The content of the compound of the present invention in the photosensitive silver halide emulsion layer is preferably 5 to 300% by weight, particularly preferably 10 to 150% by weight, based on the coupler. The content of the compound of the present invention in the non-photosensitive hydrophilic colloid layer is 1? ? /Our 0,
05-2f, preferably 0.1-1t. When the compound of the present invention is contained in both the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic cogonoid layer, the content is 50% or more in the photosensitive silver halide emulsion layer, Less than 50% by weight in the non-photosensitive hydrophilic colloid 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 step may be independent, or two or more of the steps may be performed using processing liquids that have the respective functions, resulting in a single treatment.

For example, a -bath bleach-fix solution is an example. In addition, each process can be divided into two or more times as necessary, or a combination of processes such as color development, first fixing, and bleach-fixing is also possible. In addition to the above, various steps such as a pre-hardening bath, neutralization bath, first development (black and white development), image stabilization bath, water washing, etc. are combined as necessary during the process.

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 processing → bleach-fixing processing → water washing (2) color development processing → bleaching processing → water washing → fixing processing → water washing (3) color development processing → stop → bleaching processing → water washing → water fixing processing → water washing (4) black and white Development processing → Reversal exposure → Color development processing → Bleach-fixing processing → Water washing (5) Black and white development processing → Stop → Color development processing containing a capri agent → Bleaching processing → Water washing → Fixing processing → Water washing Silver halide color photographic exposure of the present invention The processing temperature of the material processing method is set within a preferable range depending on the photosensitive material and processing prescription. Generally, the temperature is 20 to 60°C, but the silver halide color photographic light-sensitive material according to the present invention is particularly suitable for processing at 30°C 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 include N,
It is an N-dialkyl-p-phinidine diamine compound, and the alkyl group and phenyl group 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, 2-amino- 5-(N-ethyl-N-)'7
'cylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-13-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxylethylaminoaniline sulfate, 4-abano 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-)luenesulfonate and the like.

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. Color developing agent precursors are compounds that can produce color developing agents under alkaline conditions, and include Schiff base precursors with aromatic aldehyde derivatives, polyvalent metal ion complex precursors, phthalic acid imide fatty conductor precursors, and phosphoric acid amide fatty conductor precursors. Examples include precursors, sugar amine reactant precursors, and urethane type precursors.

Precursors for these aromatic primary amine color developing agents are disclosed in, for example, U.S. Pat.
, No. 507,114, No. 2,695,234, No. 3,719,492, British Patent No. 803,783,
JP-A-53-135628, JP-A No. 54-79035,
Research Disclosure Magazine No. 15,159, 1
No. 2,146 and No. 13,924. In this case, the color developing solution according to the present invention used for color developing the silver halide photographic light-sensitive material containing the color developing crude drug or its precursor may be a conventionally known alkaline processing solution (so-called activation bath or activator). liquid.) is used.

These aromatic primary amine color developing agents or their precursors need to be added in a container that can provide sufficient color development during color development processing.

This amount varies considerably depending on the type of silver halide photographic light-sensitive material, but is approximately 90% per mole of photosensitive silver halide.
．． Between 1 mol and 5 mol, preferably between 0.5 mol and 3 mol
Used in the molar range. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the 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.
They can also be added as emulsified dispersions using high-boiling organic solvents such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., or by impregnating latex polymers as described in Research Disclosure No. 14850. You can also do that.

In addition to the above-mentioned aromatic striped primary amine color developing agent, the color developing solution used in the present invention contains alkali agents such as sodium hydroxide, potassium hydroxide, potassium carbonate, trisium phosphate, and boric acid. , pI such as acetic acid (buffers, thioethers, 1-tri-3-pyrazolidones, N-methyl-p-amine phenols, known development accelerators such as polyalkylene glycols, benzyl alcohol, ethanol, phthanol) , various organic solvents such as ethylene glycol, diethylene glycol, acetone, N,N-dimethylformamide, development inhibitors such as potassium bromide and nitrobenzimidazole, sulfites, hydroxylamine,
Preservatives such as 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 developing solution 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 to 40°C.
The time is preferably 2 minutes 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, it is almost not necessary to add hependyl alcohol to the color developer, but it is not always necessary. This does not indicate that the benzyl alcohol thread 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;
per o, oil ~ 5f, preferably 0.02t ~ 2
2, more preferably in the range of 0.05f to 1f.

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. is carried out 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 using a treatment solution containing such a metal complex salt of an organic acid,
In particular, disadvantages such as precipitation of the composition and reduction in bleaching ability during storage are effectively prevented.

The metal complex salt of an organic acid in the present invention has the effect of oxidizing metallic silver produced by development and converting it into silver halide, and its structure is based on an organic acid such as aminopolycarboxylic acid, Scherer's acid, or citric acid. It is coordinated with metals such as iron, cobalt, and 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 (CIV) or CIV.

General formula (III) HOCO-A1-Z -A, -C00H General formula (5) [In each of the above general formulas, A1, A2, A3, A4, All, and A6 are each an alkylene group, a cycloalkylene group, or an arylene group. Represents a divalent hydrocarbon group such as a group. 2 is a divalent hydrocarbon group such as an alkylene group, a cycloalkylene group, an arylene group, or a -〇- group, a -8- group, or) N -A.

(A represents a monovalent hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or a lower aliphatic carboxylic acid group). ] These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Typical examples of the aminopolycarboxylic acids represented by the above general formula] or 0 are as follows.

Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-hydroxyethyl)-N
, N', N'-) diacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, ethyliminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxylmethyliminodiacetic acid, probyliuminodiacetic acid Acetic acid, butyliminodiacetic acid, dihydrogyquethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid tetra(trimethylammonium)
salt, ethylenediaminetetraacetic acid tetrasodium salt, diethylenetriaminepentaacetic acid pentasodium salt, ethylenediamine-N-(β-hydroxyethyl)-M
SN',N'-triacetic acid sodium salt, propylenediaminetetraacetic acid sodium salt, nitrilotriacetic acid sodium salt, cyclohexanediaminetetraacetic acid sodium salt, metal in the metal complex salt of an organic acid used in the present invention refers to the metal that coordinates with the organic acid. Metals that can be combined, e.g.
Metal complex salts of organic acids such as ROM, manganese, iron, cobalt, nickel, copper, etc., which are particularly preferred in the present invention, are second 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(III) ethylenediaminetetraacetate, ethylenediaminetetraacetic acid, and Iron (m) ammonium acetate.

In addition, metal complex salts of two or more organic acids with different structures may be used in combination.The specific amount used is 0.01 per 1 treatment liquid.
A range of 0.4 mol 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 alkalinolides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, solubilizers such as triethanolamine, aminopolycarboxylic acids or salts thereof, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be appropriately added.

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 tetragenide such as a thiosulfate, a thiocyanate, or a thiourea. A liquid composition containing a fixing agent 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.

In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, ammonium iodide, etc. can be used.

Silver halide fixing agents to be included in the bleach-fix solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as potassium thiocyanate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides.

The bleach-fix solution contains boric acid, borax, and
Sodium hydroxide, potassium hydroxide, sodium carbonate,
pH buffering agents consisting of various salts such as 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 fluorescent whitening agents, 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, or a type of stabilizer such as nitroalcohol nitrates, A solubilizer such as an alkanolamine, a stain inhibitor such as an organic amine, an organic solvent such as methanol, N,N-dimethylformamide, N,N-dimethylsulfoxide, etc. are 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. Or, the necessary components are replenished from the bleach-fix solution to compensate for the components carried out by the processed halogenated photographic material.

Therefore, the replenisher is usually more concentrated than the bleach or Sayama fixer, and the degree of dot-dashing depends on the amount of component being refilled or the amount of bleach or bleach-fix. Selected appropriately.

The processing time of the bleaching process and bleach-fixing process according to the present invention is 0.
．． It is preferably 5 to 2 minutes, more preferably 1 to 1.5 minutes. The treatment temperature may normally be 25 to 4QC.

In the present invention, the water washing step is usually carried out for about 2 to 4 minutes using water at a temperature of 25 to 35°C, and the amount of water used is 10 to 10 ml per 200 d of silver halide photographic material to be processed.
It is about 0 to 3000C. 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 used9. Are listed.

The photographic emulsion layer of the silver halide color photographic light-sensitive material of the present invention undergoes a coupling reaction with an oxidized product of an aromatic primary amine color developing agent during color development processing to form cyan, magenta, and yellow dyes. Among these dye-forming couplers, yellow dye-forming couplers include benzoylacetanilide type, pivaloylacetanilide type, or those in which the carbon atom at the coupling position is released during the coupling reaction. Magenta dye-forming couplers include 5-pyrazolones, pyrazolotriazoles, and pyrazolinos. A 2-equivalent magenta dye-forming coupler having a benzimidazole type, an indashilon type, or a split-off group is used, and a cyan dye-forming coupler is a 2-equivalent cyan dye-forming coupler having a phenol type, naphthol type, or a split-off group.

Among such dye-forming couplers, yellow dye-forming couplers are described, for example, in U.S. Pat.
No. 658, No. 2,875,057, No. 2.908
, No. 573, No. 2,908.513, No. 3,22
No. 7,155, No. 3.227,550, No. 3.2
No. 53,924, No. 3,265,506, No. 3,
No. 277.155, No. 3,341,331, No. 3
, 369.895, 3,384,657, 3,408,194, 3,415,652, 3,447,928, 3,551,155 ,
German Patent No. 3,582,322, German Patent No. 3,725,072, German Patent No. 1,547,868, German Patent No. 2,057
, No. 941, No. 2,162,899, No. 2,16
No. 3,812, No. 2,213,461, No. 2.2
No. 19,917, No. 2,261,361, No. 2,
263,875, JP 49-13576, JP 48-29432, JP 48-66834, JP 49-
No. 10736, No. 49-122335, No. 50-28
No. 834, No. 50-132926, No. 55-1442
No. 40 and No. 56-87041.

Also, for magenta dye-forming couplers, e.g.
U.S. Patent No. 2,600,788, U.S. Patent No. 3,061,4
No. 32, same No. 3. o No. 62,653, No. 3,127
, No. 269, No. 3,311,476, No. 3,15
No. 2,896, No. 3,419,391, No. 3,5
No. 19,429, No. 3,558,318, No. 3.
No. 684.514, No. 3.705,896, No. 3
, No. 888,680, No. 3,907,571, No. 3,928,044, No. 3,930,861, No. 3,930,816, No. 3,933,500 ,
JP-A-49-29639, JP-A No. 49-111631,
No. 49-129538, No. 51-112341, No. 52-58922, No. 55-62454, No. 55-
No. 118034, No. 56-38643, No. 56-13
No. 5841, Special Publication No. 46-60479, No. 52-34
No. 937, No. 55-29421, No. 55-35696
British Patent No. 1,247,493, Belgian Patent No. 792,525, West German Patent No. 2,156,111
It is stated in each specification of the issue.

Additionally, for cyan dye-forming couplers, e.g.
U.S. Patent No. 2,369,929, U.S. Patent No. 2.423,7
No. 30, No. 2,434,272, No. 2,474,
No. 293, No. 2.698゜794, No. 2,706
, No. 684, No. 2,772,162, No. 2,80
No. 1,171, No. 2,895,826, No. 2,9
No. 08,573, No. 3.034,892, No. 3,
No. 046,129, No. 3,227.550, No. 3
, 253,294, 3,311,476, 3,386,301, 3,419,390, 3,458,315, 3,476,563 ,
Same No. 3,516,831, Same No. 3,560.212, Same No. 3,582,322, Same No. 3,583,971
No. 3,591,383, No. 3,619,19
No. 6, No. 3,632,347, No. 3,652,2
No. 86, No. 3,737,326, No. 3.758,
No. 308, No. 3.779,768, No. 3.839
,044, West German Patent No. 2,163,811, West German Patent No. 2,207,468, Japanese Patent Publication No. 39-27563,
JP-A-45-28836, JP-A-47-37425, JP-A-50-10135, JP-A-50-25228, JP-A-50-
No. 112038, No. 50-117422, No. 50-1
No. 30441, No. 53-109630, No. 55-32
No. 071, No. 55-163537, No. 56-1938
No. 56-13643, No. 56-29235, No. 56-65134, No. 56-104333, and Research Disclosure? -(Re5search
Disclosure) 1970°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-piparyl 2
-chloro5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide 0 (Y-2) α-benzoyl-2-lychloro5-Cr-(2゜4-di-t-amyl phenocoal) butyramide] acetanilide.

(Y-3) α-benzoyl-2-chloro-5-(α-(dodecyloxycarbonyl)ethoxycarbonyl)acetanilide.

(Y-4) α-(4-carboxyphenoxy)-α-pivalyl 2
-chloro5-[α-(3-pentadecylphenoxy)
butylamide] acetanilide.

(Y-5) α-(1-benzyl-2,4-dioxo-3-imidazolidinyl)-α-bivalyl-2-chloro5-(r-(
2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-6) α-(4-(1-benzyl-2-phenyl-3゜5-dioxo-1,2,4-triaziridinyl)]-]α-bivalyl-2-chloro I: I-5-[γ -(2゜4-G-t
-amylphenoxy)butyramide]acetanilide.

(Y-7)
amylphenoxy)butyramide]henzoyl)-2-
Methoxyacetanilide.

(Y-8) α-(3-[α-(2,4-di-t-amylphenoxy)butylabado]benzoyl)-2-methoxyacetanilide.

(Y-9) α-(4-(4-benzyloxyphenylsulfonyl)
phenoxy]-α-bivalyl-2-chloro-5-[γ-
(2,4-di-t-amylphenoxy)butyramide]
Acetanilide.

(Y-10) α-Vivalyl α-(4,5-dichloro-3-(2H)
-pyridazol-2-yl)-2-chloro-5-((hexadecyloxycarbonyl)methoxycarbonyl]acetanilide.

(Y-11) α-Vivalyl α-(4-(p-chloroαphenyl)-5
-oxo-Δ-atofucillin-1-yl)-2-chloro-5-[α-(dotecyloxycarbonyl)ethoxycarbonyl]acetanilide.

(Y-12) α-(2,4-dioxo-5,5-dimethyloxazolidin-3-yl)-α-bivalyl-2-chloro-5-[
α-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-13) α-Biparyl α-(4-(1-methyl-2-phenyl-3,5-dioxo-1,2,4-)riSiligel)
]-]2-chloro5-γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-14) α-hyhalyl α-[4-(p-ethylphenyl)-5
-oxo-12-tetrazolyl-1-yl]-2-chloro-5-Cr-(2,4-di-t-amylphenoxy)
butylamide] acetanilide.

(Y-15) α-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-)riazolidinyl)-α-pivalyl 2
-Chloro 5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide.

(M-1) 1-(2,4,6-)lichlorophenyl)-3-(3-
(2,4-di-t-amylphenoxyacetamide)penzamidocou-5-pyrazolone.

(M-2) 1-(2,4,6-)lichlorophenyl)-3-(3
-dodecylsuccinimidobenzamide)-5-pyrazolone.

(M-3) 4.4'-methylenebis(1-(2,4,6-trichlorophenyl)-3-(3-(2,4-di-t-amylphenol diacetamide)benzamide to 5-pyrazolone ).

(M-4) 1-(2,4,6-trichlorophenyl)-3-(2-
/ Roro 5-octadecyl succum imide anilino)-
5-Pyrazolone.

(M-5) 1-(2-di-4,6-dimethylphenyl)-3-
(3-(α-(3-pentadecylphenoxy)butyral ξdo]penzamide)-5-pyrazolone.

(M-6) 1-(2,4,6-)lichlorophenyl)-3-(2-
/lower 5-octadecylcarbamoylanilino)-5
-Pyrazolone.

(M-7) 3-ethoxy-1-(4-(α-(3-pentadecylphenoxy)butyramido]phenyl)-5-pyrazolone.

(M-8) 1-(2,4,6-)lichlorophenyl)-3-(2-
Chloro-5-tetradecanamide anilino)-5-pyrazolone.

(M-9) 1-(2,4,6-)lichlorophenyl)-3-(2
-Chloro-5-[α-(3-t-butyl-4-hydroxyphenoxy)tetradecanamide anilino)-5-pyrazolone.

(M-10) 1-(2,4,6-)lichlorophenyl)-3-(3-
(2,4-di-t-amylphenoxyacetamide)penzamide-4-acetoxy-5-pyrazolone.

(M-11) 1-(2,4,6-)lichlorophenyl)-3-(3-
(2,4-di-t-amylphenoxyacetomido)penzamide]-4-ethoxycarbonyloxy-5-pyrazolone.

(M-12) 1-(2,4,6-)lichlorophenyl)-3-(3-
(2,4-di-t-amylphenoxyacetamide)penzabad)-4-(4-chlorocinnamoyloxy)
-5-pyrazolone.

(M-13) 4.4'-benzylidenebis((1-2,4,6-)lichlorophenyl)-3-(2-chloride-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-/rollo5-
[γ-(2,4-di-t-amylphenoxy)butyramide]anilino)-5-pyrazolone]C(M-15) 4,4'-(2-chloro)benzylidenebis[1-(
2,4,6-)dichlorophenyl)-3-(2-chloro-5-dodecylsufciimidoanilino-5-pyrazolone].

(M-16) 4.4'-methylenebis(1-(2,4,6-)dichlorophenyl)-3-(3-[:α-(2,4-di-t-
amylphenoxy)butyramide]penzamide)-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-)dichlorophenyl)-3-(4-
Nitroani IJ/)-5-Hy5zolone.

(M-20) 1-(2,4,6-)dichlorophenyl)-3-(2-
Chloro-5-octadecenylsfuciimide-anilino)
-5-pyrazolone.

(M-21) 1-(2,4,6-)dichlorophenyl)-3-(2-
Chloro-tridecanamido-anilino)-5-pyrazolone.

(M-22) 1-(2,4,6-)dichlorophenyl)-3-(2-
Chloro-5-tetradecanamido)anilino-4-(2
-dodecylamide) phenylthio-5-pyrazolone.

(M-23) 1-(2,4,6-)dichlorophenyl)-3-[2
-chloro-5-(2,4-di-t-amylphenoxy)
Acetamide] Anilino 4-phenylthio-5-pyrazolone.

(M-24) 1-(2,4,6-)dichlorophenyl)-3-(2-
Chloro-5-tetradecanamido)anilino-4-(2
-methoxy)phenylthio-5-pyrazolone.

(M-25) 1-(2,4,6-)dichlorophenyl)-3-(2-
Chloro-5-tetradecanamido)anilino-4-benzylthio-5-pyrazolone.

(C-1) 1-Hydroxy-N-[δ-(2,4-di-1-amylphenoxy)butyl-2-naphthamide 0 (C-2) 2.4-dichloro-3-methyl-6-(2, 4-G 1
-amylphenoxyacetamide)phenol.

(C-3,) 2.4-dichloro-3-methyl-6-[α-(2゜4-
di-t-amylphenolic)butyramide]phenol.

(C-4) 1-Hydroxy-4-(3-nitrophenylsulfonamide)-N-(δ-(2,4-di-monoamylphenoxy)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-Perfluorobutylabado 5-[α-(2,4-
C t -/milphenoxy)hexaneamidesiphenol.

(C-8) 1-Hydroxy-4-(4-nitrophenylcarbamoyl)oxy-N-[δ-(2,4-di-t-amylphenoloxy)butyl-2-naphthamide.

(C-9) 2-(α, α, β, β-tetrafluoropropionamide-5-[α-(2,4-di-t-amylphenoxy)
butylamide] 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-Cδ-(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-Rio-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-acetylaminocophenol.

(C-16) 2-(4-cyanobenzoyl)amino-4-chloro-5
-[α-(2-dodecylsulfonamino)-α-dimethyl-acetylaminocophenol.

(C-17) 2-(perfluorobenzoyl)amino-4-chloro-
5-[α-(3-dodecylsulfonamino)-α-butyl-acetylaminocophenol.

(C-18) 2-(perfluorobenzoyl,)amino-4-chloro-5-((2,4-di-t-butylphenoxy)acetylamino]phenol.

(C-19) 2-pensoylanilino-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 organic solvent, the preferred high-boiling organic solvent is an organic solvent that is immiscible with water and has a boiling point of about 170°C or higher; Examples include phthalate esters (dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diallyl phthalate, dinonyl phthalate, dilauryl phthalate, dibenzyl phthalate, diallyl phthalate e), phosphoric 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, benzoate, etc.) octyl acid, etc.), alkylamides (diethyl laurylamide, etc.), sepatic acid esters (diethylhexyl cepatate, etc.), stearic acid esters (butyl stearate, etc.), maleic acid esters (dinonyl maleate, etc.), succinic acid esters (succinic acid esters), diethyl acid, 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 that can be used as auxiliary solvents in conjunction with such high boiling point organic solvents include:
Lower acetylacetate (ethyl acetate, butyl acetate, β
-ethoxyethyl acetate, etc.), butyl alcohol,
Examples include methyl isobutyl ketone, chloroform, hexane, cyclohexane, 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, back mixing method, conversion method, etc. Silver halide grains may be manufactured, and silver halide grains with or without boundaries between different halogen compositions can be effectively used in the present invention.

The most common binder used in the photographic constituent layer of the silver color photographic light-sensitive material of the present invention is gelatin such as alkali-treated gelatin or acid-treated gelatin. gelatin,
derivative gelatin, such as phenylcarbamoyl gelatin;
Albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, 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 includes ruthenium,
Noble metal sensitization with salts of noble metals such as rhodium, palladium, iridium, platinum, gold (e.g. ammonium chloroparadate, potassium chlorovaladite, potassium chlorovaladite, potassium chloroaurate, etc.), activated gelatin, unstable sulfur [ Sulfur sensitization with arsenic compounds (e.g., thiosulfate, IJium, etc.), selenium sensitization with selenium compounds, or stannous salts, polyamines, etc. and low pA
Chemical sensitization such as carrier sensitization under g conditions can be performed.

Furthermore, 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. 39,201, No. 2,072,908, No. 2,
No. 739,149, No. 2,213,995, No. 2
, 493.748, specification described in 2,519,001, West German Patent No. 929,080, British Patent No. 50
The cyanine dyes, merocyanine dyes, or composite cyanine dyes described in each specification of No. 5,979 can be used alone or in combination of two or more. These various optical sensitizers are used for purposes other than their original purpose, such as preventing capri, 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, benzothiazolium compounds, zinc compounds, cadmium compounds, and mercaptans can be used as long as they do not impair the effects of the present invention.

Furthermore, 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 alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkyl succinate sulfonate, polyalkylene compounds, etc.), water-soluble anti-irradiation dyes (for example, azo compounds, styryl compounds, oxynol compounds, anthraquinone) type compounds and triphenylmethane type compounds, etc.), hardening agents (e.g., halogen-substituted S-)! J azine compounds, active vinyl compounds, ethyleneimino compounds, epoxy compounds, water-soluble aluminum salts, etc.), film property improvers (e.g. glycerin, polyalkylene glycols,
Polymer aqueous dispersions (such as latex), solid or liquid paraffins, 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; Depending on the purpose, a laminate of two or more substrates, such as a laminate with polypropylene and polypropylene, etc., can be used as appropriate. 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 a specific solvent, which has been subjected to surface treatment such as electron impact treatment or flame treatment, or which has been subjected to subbing treatment such as providing a subbing layer.

Each constituent layer of the silver halide color photographic light-sensitive material is coated onto this support by a commonly known coating method, such as dip coating, roller coating, bead coating, curtain flow coating, etc. and then dried.

■ Specific Examples of the Invention Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 Six types of halogenated/silver color photographic light-sensitive materials (comparative samples IA to 6A) were prepared by sequentially coating the following layers on a paper support coated with polyethylene from the support side.

In addition, in all the examples below, the amount added is expressed as the amount of 1-1 unless otherwise specified.

Layer 1: 2.1 t of gelatin, 0.35 f (in terms of silver) blue-sensitive silver chlorobromide emulsion (85 moles of silver bromide, average grain size: 0) .65 ttm), and 1.2xlO moles of the yellow coupler shown in Table 1 and 0.015F of 2.5-ttm.
- A layer containing 0,31 dioctyl heptatalate (hereinafter referred to as DOP) in which octylhide tetraquinone (hereinafter referred to as HQ-1) is dissolved.

Layer 2: Gelatin retention layer containing 1.32 gelatin and 0.05 F bisvinylsulfonyl methyl ether.

On the other hand, in the comparative samples (IA to 6A), in layer 1,
Silver halide color photographic materials of the present invention (samples 1B to 6B of the present invention) which were the same as the above comparative samples except that they contained 0.4 of the exemplified compound (E-3) of the present invention were prepared. still,
This exemplified compound E-3 was dispersed in gelatin at the same time as the above yellow coupler.

Six types of comparative samples (IA to 6A) obtained in this way
After exposing six types of samples (IB to 6B) of the present invention through an optical wedge, they were processed in the following steps.

The color developing solution diagram shows a normal color developing solution containing benzyl alcohol and ethylene glycol for dissolving this, and the color developing solution () does not contain benzyl alcohol and ethylene glycol.

The processing steps, temperature, time, color developing solution used, and composition of the bleach-fixing solution are as follows.

Color developer (J3) A color developer from which ethylene glycol and benzyl alcohol have been removed.

Bleach-fix solution 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, r is reflection density 0.
5 to 1.5 gradation, relative sensitivity is exemplified compound E of the present invention
The relative sensitivities of comparative samples (IA to 6A) which do not contain t-benzyl alcohol when treated with a color developer (4) containing t-benzyl alcohol, with each sensitivity set to 100, are shown.

Margin Table-1 Below, from the results shown in Table-1, samples IB to 6B of the present invention did not achieve any of the following traps: high contrast, sensitization, and maximum density when processed with a color developer (g) containing benzyl alcohol. Also, it can be seen that good photographic properties are obtained even when processing with a color developer (B) containing no benzyl alcohol.

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) l-1...,...
...2.12 gelatin, 0.28F red-sensitive silver chlorobromide emulsion (silver bromide composition 65 moles, average grain size 0.35 μm), and 0.42F cyan coupler C-15. A layer containing 0.12f DOP in which 0.005f HQ-1 was dissolved.

1 m2...Gelatin protective layer containing 1.31 gelatin and 0.05f bisvinylsulfonyl methyl ether.

Furthermore, Samples 8 to 16 were prepared in the same manner as Comparative Sample 7, except that 0.28y of the compound shown in Table 2 was contained in Layer 1 in Comparative Sample 7.

The ten types of samples 7 to 16 obtained were treated in the same manner as in Example 1 to obtain the results shown in Table 2.

Table-2 Comparative compound-1 (t)C4H7OCR2CH20CH2CH2QC4H
, (t) Comparative compound-2 Comparative compound-3 (n) C,8k137-0-C18H37(n) Table-
From the results shown in 2, when Samples 11 to 16 of the present invention were processed with the color developer (5) containing benzyl alcohol, good results were obtained in both high contrast and maximum density. It can be seen that good gradation and maximum density characteristics can be obtained even when processing with a color developing solution containing no alcohol.

Example 3 After corona discharge was applied to a paper support coated with polyethylene on both sides, the following seven layers were sequentially applied from the support side,
A multilayer color photographic paper was created.

(Comparative sample 17) Layer 1 1.5 f of gelatin, 0.33 t (in terms of silver) of blue-sensitive silver chlorobromide emulsion (silver bromide 85 mol) (average particle size 0.65 μm), 0.6×10 mol of yellow coupler (Y-5) and 0.9×10 mol of yellow coupler (Y-5).
15) and 0.015r(7) HQ-1 dissolved
, a layer containing a DOP of 25r.

Layer 2: Layer containing 0.06f DOP in which 0.92 gelatin and 0.09f HQ-1 are dissolved.

Layer 3: 1.3 f gelatin, 0.27 F (in terms of silver) green-sensitive silver chlorobromide emulsion (70 moles of silver bromide, average grain size 0) layer containing DOP in which 0.59 x 10 moles of magenta coupler (M-4) and 0.015 f of HQ-1 were dissolved.

Layer 4: 1.51 gelatin, 0.8F ultraviolet absorber UV-1 shown below, and 0.8F gelatin.
A layer containing 0.6f DOP in which 041 HQ-1 is dissolved.

Layer 5: 1.3t of gelatin, 0.3F (in terms of silver) red-sensitive silver chlorobromide (silver bromide 6
5 moles, average particle size 0.35 μm), 0.75×10 moles of cyan coupler (C-3) and 0.00! A layer containing 0 and 2f DOP obtained by fermenting M HQ-1.

1 fin 6・・・・・・・・・・・・1. Or gelatin, 0.2f ultraviolet absorber UV-1 and 0.018'
A layer containing 0.015f DOP in which HQ-1 of 0.015f is dissolved.

Layer 7・・・・・・・・・・・・1. A layer containing Of gelatin, 0.015t 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 in the coupler dispersion of Ni1 In the coupler dispersion of layer 5, the exemplified compound E-5 of the present invention was added in an amount of 70% by weight based on the coupler.
Sample 19 was prepared in the same manner as Comparative Sample 17 except that the following components were added.

After the obtained samples 17 to 19 were exposed to white light, they were treated with a color developing solution and a homogenizer in the same manner as in Example 1. The obtained results are shown in Table 3.

In the table, BSG and R indicate the results of density measurements using blue, green, and red monochromatic lights, respectively.

Table 3 From the results shown in Table 3, color photographic paper sample 18 of the present invention
It can be seen that samples No. 1 and No. 19 had good gradation and maximum density even when processed with the color developer (B) not containing benzyl alcohol.

Example 4 The three color photographic papers used in Example 3, Samples 17, 18 and 19, were exposed to a fluorescent lamp for 2 seconds and then subjected to color development in the aforementioned color developer for 3 minutes and 30 seconds. It was treated with a fatigue bleach-fix solution at 33° C. for 1 minute and 30 seconds, then 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 Bleach-fix solution 1 used in Example 1 was applied, 20 m of a 10% silver nitrate aqueous solution was added, and the oxidation-reduction potential was adjusted to -100 mV (comparison electrode: silver-silver chloride monopolar).

Margin Table-4 Below From the results shown in Table-4, samples 18' and 19 of the present invention
It can be seen that even when processed with a fatigued bleach-fix solution, '' maintains a good maximum red density with almost no cyan leuco dye being produced.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material 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 CI) and [■]. Processing method for silver chemical color photographic materials. General formula CI) R, -0-R2 General formula [■] R3-0 + CH2 No. 0-R4 (In the formula, R1 and R2 each represent an alkyl group, and R8 and R4 each represent an alkyl group, n represents 2t or 3.)