JPH02294641A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To lessen bleach fogging even in a rapid processing by conforming the pH of a processing bath for the desilvering processing to <=5.0 at the time of subjecting the material contg. a high boiling org. solvent having <=6.0 dielectric constant into a red sensitive silver halide photosensitive layer to an imagewise exposing, then to color developing, desilvering and fixing processings. CONSTITUTION:This photosensitive material has respectively at least one layer of the red sensitive silver halide photosensitive layer, green sensitive silver halide photosensitive layer and blue sensitive silver halide photosensitive layer on a base and the dry film thickness of a nonphotosensitive layer provided between the photosensitive layer nearest the base and the under coating layer of the base is <=2.5mum. The pH of the processing bath of the desilvering processing is <=5.0 at the time of subjecting the silver halide photographic sensitive material contg. the high boiling org. solvent having <=6.0 dielectric constant in the red sensitive silver halide photosensitive layer to the imagewise exposing then to the color developing, desilvering and fixing processings. The bleach fogging is lessened in this way when the rapid processing is executed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an image forming method for a silver halide color photographic light-sensitive material, and particularly to an image forming method related to the image quality of a color photographic material. (Prior Art) Generally, the basic steps for processing color photochromic materials are a color development step and a desilvering step. In the color development process, silver halide exposed to light is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a coloring agent (coupler) to form a dye image. In the next desilvering process,
The silver produced in the color development process is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved by a silver ion oxidizing agent, commonly called a fixing agent. By going through this desilvering process, only a dye image is created on the color photosensitive material. The above desilvering process is carried out in two baths, a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, or in one bath using a bleach-fixing bath containing both a bleaching agent and a fixing agent. There is. In addition to the basic steps mentioned above, the actual development process includes various auxiliary steps to maintain the photographic and physical quality of the image, or to improve the preservation of the image. Examples include a hardening bath, a stop bath, an image stabilization bath, and a water washing bath.

In recent years, with the spread of small in-store processing service systems called minilabs, there has been a strong demand for shortening the time required for the above processing in order to quickly respond to customer processing dependencies. In particular, the highest demand was to shorten the desilvering process, which conventionally occupied most of the processing time. However, the ferric complex salt of ethylenediaminetetraacetic acid, which is the mainstream bleaching agent used in bleaching solutions and bleach-fixing solutions, has a fundamental drawback of weak oxidizing power, so various improvements such as the use of bleach accelerators have been made. Despite the addition of the above requirements, the above requirements have not yet been met. On the other hand, as bleaching agents with strong oxidizing power, red blood salt, dichromate, ferric chloride, persulfate, bromate, etc. are known. The reality is that they each have many drawbacks from the viewpoint of gender and other factors, and cannot be widely used for over-the-counter processing. Under these circumstances, pH containing ferric sulfate of 1,3-diaminobrobantetraacetic acid described in JP-A No. 62-222252
A bleaching solution of about 6 has a higher oxidizing power than a bleaching solution containing ferric ethylenediaminetetraacetic acid salt and can bleach silver more quickly, but it does not require an intermediate bath after color development. Direct bleaching has the disadvantage of causing color fog called bleaching. Apart from this problem of bleaching power, a new problem arises when processing by shortening the bleaching time with this bleaching solution, that is, a large increase in staining occurs during storage of the processed photographic material. It has also become clear. One way to solve the above problem is to reduce the amount of components remaining in the film of the photosensitive material after image formation, that is, immediately before the desilvering process, and even after the completion of all processing. Although it would be possible to increase the number of processing steps and lengthen the processing time, this solution is not acceptable as it goes against the industry's desire for laboratory operators and users to speed up processing. Also, on the other side, European Patent Publication No. 255,722,
Same No. 258,662, Same No. 228,655, Same No. 2
No. 30,048 and U.S. Pat. No. 4,704.350 using compounds that react with the developing agent itself and/or the oxidized form of the developing agent, respectively, to give a substantially colorless product. It has been proposed to prevent staining by However, the use of these compounds is related to magenta couplers, especially virazoloazole magenta couplers, and although their effects are certainly recognized, their effects are not sufficient, and when their amounts are increased, they impede photographic performance, especially color development. It was found that this caused a decrease in sensitivity and a change in gradation.
Therefore, it is extremely difficult to use these compounds in color photogenic materials for photography, and it is currently necessary to consider other approaches to solving the above problems. (Problems to be Solved by the Invention) It is an object of the present invention to provide a photosensitive material that exhibits less bleaching power even during rapid processing.Furthermore, even when the color image is stored for a long period of time, stains remain in uncolored areas. Another object of the present invention is to provide a luminescent material with less increase in bleaching power.Furthermore, it is an object of the present invention to provide a processing method with less bleaching power when rapid processing is performed using the luminescent material. (To solve the problem The present inventor has found that the above object can be achieved by the method described below. At least one red-sensitive silver halide light-sensitive layer, a green-sensitive silver halide light-sensitive layer and a blue-sensitive silver halide light-sensitive layer are provided on a support. The dry film thickness of the halogenated photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer on the support is 2.
．． Less than 5p, red malignant halogenation! II When a silver halide color photographic light-sensitive material containing a high boiling point organic solvent with a dielectric constant of 6.0 or less in the photosensitive layer is subjected to color development, desilvering, and fixing treatment after imagewise exposure, the desilvering treatment is performed. The pH of the treatment bath is 5.
．． A method for processing a silver halide color photographic material, characterized in that the silver halide color is 0 or less.

The photosensitive material and image forming method of the present invention will be described below. The present invention relates to a color negative photosensitive material for general use and movies (hereinafter simply referred to as photosensitive material). In the light-sensitive material of the present invention, the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer of the support is usually a silver halide photosensitive layer coated directly on the undercoat layer of the support. It means that it will not be done. In photosensitive materials, another layer different from the undercoat layer may be provided on top of the undercoat layer to improve the physical properties of the layer, such as the adhesion to the support, of the layers that are sequentially coated.
and/or the light passes through the upper photosensitive layer (layer containing silver halide grains and a coupler dispersion) during shadowing, called an antihalation layer, while being diffused, and the light that reaches the support surface partially or entirely. It reflects back to the light layer,
A layer may be provided to prevent re-exposure of the cut point from the point of initial incidence, and/or an antihalation dye, colloid daughter, or other material incorporated into the antihalation layer may be applied to the antihalation layer. A so-called intermediate layer is provided to prevent the various compounds used for the purpose from adversely affecting the upper photosensitive layer that is sequentially coated. The non-photosensitive layer is a general term for each of these layers. Specific examples of these layers include (support, one undercoat layer), one intermediate layer (1), one antihalation layer, one intermediate layer (2), (support one, undercoat N), one antihalation layer, one intermediate layer 1i.
1 (1) (support, one undercoat layer), one intermediate layer, (1) one antihalation layer (support, one undercoat N), and one antihalation layer.

The total dry film thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support of these photosensitive materials and the undercoat layer of the support is determined by the layer structure as mentioned in the above specific example depending on the performance provided to the photosensitive material. The membrane thickness is determined. Most of the photosensitive materials currently on the market have a dry film thickness of 2.51 or more. The dry film thickness mentioned here will be explained later. Concerning image forming processing of photosensitive materials, in order to meet the strong demands of laboratory operators and users in the industry for speeding up the processing, intensive research efforts have been made day and night. Processing steps after the development processing step (
If you shorten the processing time (washing or rinsing process, desilvering process, washing and/or stabilization process), the minimum density (Dmin) of the last exposed part of the photosensitive material will increase (hereinafter referred to as bleaching fog) and Problems such as a large increase in stain in unexposed areas occurred when images were saved after processing, which turned out to be a major obstacle to speeding up processing. When we clarified the reason for this, we found that in the layer structure of the photosensitive material, if the thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat N7 of the support was large, Ds+in surprisingly increased. It was confirmed that there was a large increase in stain during image storage. From this fact, it is preferable to reduce the total thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer of the support, and in the present invention, this total thickness is reduced to 2.
The film thickness is preferably 5μ or less, more preferably 2.0μ or less, and most preferably 1.5μ or less. Further, the lower limit of the total film thickness can be reduced within the range where these layers do not impair the performance of the photosensitive material. Therefore, the lower limit is not particularly limited.

The film thickness of the multilayer silver halide color photographic light-sensitive material in the present invention is measured by the following method.

The photosensitive material to be measured is stored under conditions of 25°C and 50% R}I for 7 days after its preparation. First, measure the total thickness of this photosensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to determine the total thickness of the photosensitive material excluding the support. The film thickness shall be . This thickness can be measured using, for example, a film thickness measuring device using a contact type piezoelectric transducer (AnritsuEIecLrjc Co. Ltd.
d,, K-4028 SLand. ) can be used for measurement. The coating layer on the support can be removed using an aqueous sodium hypochlorite solution. Next, using a scanning electron microscope, a cross-sectional photograph of the above-mentioned light-sensitive material is examined at its highest point (preferably the magnification is 3.000 times or more).
Then, the total thickness on the support and the thickness of each layer were actually measured, and the total thickness measured by the film thickness measuring device (absolute of the measured thickness {i
) can calculate the thickness of each layer. Swelling rate (
(see formula below) is preferably 50 to 200%, and 70 to 150%.
% is more preferable.

'1t T. : Equilibrium swelling film thickness T. at 25°C in HtO. :25
If the dry total film thickness swelling rate at 55% till at 55% °C deviates from the above values, the amount of remaining developing agent will increase, and this will have a negative impact on photographic performance, image quality such as derooting ability, and film properties such as film strength. It turns out.

However, even with photosensitive materials in which the total thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer is reduced to 2.5 mm or less, there is still an increase in DIain and staining. The increase is not sufficiently contained. After investigating the causes of these problems, we found that the process after the color development process, especially the omission of water washing or rinsing before or during the grudge removal process, and the shortening of the process time, caused an increase in Dmin and staining. It has become clear that this is a big deal.

Among these, the increase in Dmin occurs during the processing process. When the photosensitive material is transported to the bleaching bath in the desilvering process, if a developing drug is present in the film, colloidal silver and developed silver will be ionized or rehalogenated. In the so-called silver bleaching process, the developing agent present is partially oxidized to form quinone diimine (
This reacts with the uncolored coupler remaining in the film of the photosensitive material to form a dye.
■We have clarified that in increases. This fact can be easily confirmed by observing an increase in magenta density when various treatments are performed and the resulting Dmin is measured using green light. It can also be recognized that the increase is large compared to the increase in temperature. In addition, stains that occur when photosensitive materials are stored for long periods of time after processing are caused when the developing agent remaining in the film is oxidized by oxygen that permeates through the film of the photosensitive material, and a portion of the stain is oxidized. It may form a dye through a fogging reaction with the remaining uncolored fogler, or T' may form other compounds such as dimers, and these compounds may have absorption in the visible range. It is presumed that this results in an increase in staining.

Because the increase in magenta Dmi + Jl degree after processing is particularly large, and because human visibility is normal in the magenta region,
It is important to reduce this increase in magenta Dmin'a degree.

Therefore, as a result of further investigation, in addition to thinning the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer of the support, we decided to reduce the thickness of the red light-transmitting layer by adding a coupler and other substances to the layer. High boiling point organic solvent (oil) used to disperse the material
It has been found that using a compound with a low dielectric constant as a bleaching agent reduces the bleaching effect. It was completely unexpected that the problem of bleaching power caused by magenta coupler color development was affected by the properties of the dispersion oil used in other layers. Therefore, in the present invention, the high boiling point organic solvent for dissolving and dispersing the coupler used in the red sensitive layer is preferably a compound having a dielectric constant of 6.0 or less, more preferably 6.0 or less and 1.9 or more. It is a high boiling point organic solvent. Further, the high boiling point organic solvent may be a mixture of two or more types. Note that the dielectric constant in the present invention refers to the dielectric constant at 25°C, and this value can be easily determined by measuring with the transformer bridge method (Ando Electric TRS-107).

Examples of the high-boiling point solvent used in the present invention include those represented by the following general formulas (A), (B), (C), (D), or (E). General formula (A) General formula (B) w, -coo-w, one ritual (C) General formula (D) General formula (E) W, -O-W. (In the formula, W,, W. and 6 are respectively HA or an unsubstituted alkyl group, a cycloalkyl group, an alkenyl group,
represents an aryl group or a heterocyclic group, W, hamo, 0-1
or S-W, where n is an integer from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other, and in -a formula (E), 匈, and 6 are condensed. May form a ring. ) The high boiling point organic solvent used in the present invention has the above general formula (A), (B), (C), (D) or (E
) in the high boiling point organic solvent represented by substituent-1,
The sum of 6 or 1 carbon atoms is the general formula (A), (
Compounds having B), (C), (D), or (E) of about 8 or more and having a dielectric constant of 6.0 or less are applicable.

In the general formula (A), (B), (C) or (E), H. , Kayo and 6 have a substituent, this R'(
(R' is 2~ formed by removing a hydrogen atom from a phenyl group
It may be a group having a bonding group selected from (indicating a hexavalent group) and -0-. In general formula (A), (B), (C), (D) or (E), the opposite W. , W. Ori. The alkyl group represented by may be either straight chain or branched. For example, methyl, ethyl, proyl, butyl, bentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebutadecyl, octadecyl, nonadecyl,
Eikosir et al. The permissible substituents for these alkyl groups are represented by the general formula (
To explain the case of A), for example, a halogen atom, a cycloalkyl group, an aryl group, an ester group, and examples of such substituted alkyl groups include halogen (
F, CI, Br) substitution products (1C!O., -CsLFs
, -C*HsP+h, -CzHaCI! ,C2H@C
l, -CsHgClz, -C=HsCffiBr
, -CJsBrz, etc.), ClhCl{zcOOc+J
ts, -(CHz)4cOOcth(Ch)411,
- (CHz) tcOOcJq, - (Clh) s
cOOcaHq etc.),? Substituents that give malic acid esters, etc. (-CIlCH(Of{)-COOCaH, 3, etc.)
, tartaric acid ester, etc. What is the aryl group represented by substituent W1, h, 6, or h? 01
1■C(OH)CLCOOCstl+. etc.

COOC. I4. Also in general formulas (B) to (E), the same substituents as in the alkyl group of general formula (A) are added to the alkyl group if
! 10. Furthermore, in general formula (E), 1. and 6 may be an oisilane ring, an oxolane ring, or an oisane ring forming a condensed ring. Cycloalkyl C1 represented by W1, h, 6 or W4
1, phthalic acid such as Cfl, isophthalic acid, terephthalic acid, trimellitic acid ester, etc., and substituted benzoic acid esters such as.

7ru))-nil4 is -C4To, -CSH? , -C6H
l+, -CJ+s, -CsH+s, -c, eL? ,
-CI11{23, -CIlH35, etc., and direct alkenyl groups are, for example, halogen atoms (F, CI, Br
), -0CsH+,, -0C+t}lts-? 1■H
! Substituted alkenyl groups such as 3, phosphate ester solvents such as 7-methyloctyl phosphate and tricyclohexyl phosphate, phenolic solvents such as 2,5-di-Lert-amylphenol and 2,5-di-sec-amylphenol, etc. can be mentioned. The general formulas (A), (B), (C), (D) and (
The dielectric constant represented by E) is 6. (Specific examples of high boiling point organic solvents of 1 or less are shown below, but are not limited to these. (S-1)) General formulas (A), (B), (C), (D) and ( The high boiling point organic solvent according to the present invention represented by E) can be used alone or in combination, or in combination with other conventionally known high boiling point solvents, as long as the purpose of the present invention can be achieved. Known high boiling point organic solvents include, for example, tricresyl phosphate, tri-2-ethylhexyl phosphate, (S-3) (S (S-6) (S-7) (S (S-14) (S (S (S-17) (S (S-9) (S (S-11) (S-12) (S-13) C.H% C. II s (S-19) (S-20 ) (S (S-22) (S-23) (S-24) (S-29) (S-25) rl CJ+1 (S-26) (S-31) (S-27) ?JIgCOOC+oHz+-n I HO-C-COOC+.H■ichiro ε=4.83 ?H2COOCI.H■ichiro (S-28) C.Hth+-f1 n-C+J*tCOOCHgCH-CsH+t-n
( = 2.89 (S-32) The high boiling point organic solvent of the present invention can be used by being added to the layer containing red-sensitive silver halide and the adjacent non-photosensitive layer. a layer containing sensitive silver halide;
and relative to the total amount of coupler contained in the adjacent non-photosensitive layer! ! The quantitative ratio is preferably 0.01 to 20, and particularly preferably 0.03 to 10. Anionic surfactants and nonionic surfactants can be used as dispersion aids when dissolving the coupler and/or other organic materials in these high-boiling solvents and dispersing them into the gelatin solution using mechanical or ultrasonic waves. Active agents and cationic surfactants can be used. It can also be used as an auxiliary solvent when dissolving organic materials such as couplers in high boiling point organic solvents.
Low boiling point solvents such as ethyl acetate, butyl acetate, and ethyl propionate may also be used. The following image forming method of the present invention will be explained.

The pH of the bleaching solution used in the present invention is 5.0 or less. As mentioned above, a bleaching solution containing ferric stirrup salt of 1,3-diaminopropanetetraacetic acid (1,3-DPTA-Fe) has to be adjusted to a pH level from the viewpoint of both ensuring the bleaching speed and preventing poor recoloring of the cyan dye.
A value around 6.0 has been considered optimal. However, by using the photosensitive material having the structure of the present invention, 1.3-DPTA・
It has been found that bleaching using an oxidizing agent such as Fe at a pH of 5.0 or less can speed up the process without causing post-treatment stains or poor color recovery. This has resulted in rapid processing with less post-processing stains.

Furthermore, when the photosensitive material of the present invention was processed by the above-mentioned processing method, it was surprisingly found that it was highly effective in reducing the increase in stain during image storage after processing. The preferred ρ{1 range of this bleaching solution is 5.0 or less, more preferably 4.0 or less. As the oxidizing agent used in the bleaching bath of the present invention, 1.3-diaminoprobanetetraacetic acid ferric complex salt (1.3-DPTA・Fe
), 1.4-butylenediaminetetraacetic acid ferric complex salt, glycol ether diamine tetraacetic acid ferric salt, iminodiacetic acid ferric salt, methyliminodiacetic acid ferric complex salt,
N-(2-acetamido)iminodiacetic acid ferric complex salt, diethylenethioethertetraacetic acid ferric complex salt, ethylenediaminetetraacetic acid ferric salt (EDTA Fe), diethylenetriaminetetraacetic acid ferric complex salt, trans-1.2 -Cyclohexanediaminetetraacetic acid ferric complex salt, etc. can be used. Among these, particularly preferred oxidizing agents are pH
The redox potential at 6.0 is 150lllV (vs.
NHE) The above is nomonoteal. Specifically 1.3-DP
TA-Fe and glycol ether diamine tetraacetic acid ferric complex salts have particularly excellent oxidizing power and are very effective in speeding up the bleaching process. In addition, when using the conventionally used EDTA-Fe, the oxidation-reduction potential is 150 m
Since it has a weaker oxidizing power than V, there is a problem with derooting properties during rapid processing, so it is not very preferable.

Therefore, in the present invention, using 1,3-T^Fe or glycol ether diaminotetraacetic acid ferric complex salt,
Processing the photosensitive material of the present invention at a pH of 5.0 or less is
Most preferred from the viewpoint of reducing bleaching fog and rooting properties. The redox potential at pH 6.0 used in the present invention is Tr
analysisSor the Faraday
It was measured using a method similar to that described in Society+ 55 (1959).

1.3-1) Ferric aminopolycarboxylic acid represented by PTA/Fe! The total amount of F salt added is preferably from 0.1 mol to 1.0:r/l, preferably from 0.15 mol.
(1.7 mol/2, most preferably 0.25 mol to 0.
7 moles/7! The range is . To maintain the pH of the bleach solution at 5.0 or less, organic acids such as acetic acid, citric acid, and malonic acid, as well as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid, can be used. Dissociation constant (
Acids with pK a) in the range of 2.5 to 5.5 are preferred from the viewpoint of imparting buffering properties to the region of the present invention, and in addition to the acetic acid, citric acid, and malonic acid, acetic acid, C, fric acid, and formic acid are preferred. Examples include various organic acids such as , butyric acid, malic acid, tartaric acid, oxalic acid, monolobionic acid, and phthalic acid. Among these, acetic acid is particularly preferred.

The amount of these acids used is preferably 1.0 mol or more, particularly preferably 1.5 mol or more, per 1 liter of bleaching solution. The oxidizing agent used in the bleaching solution may be used alone or in combination with other oxidizing agents.

The above aminopolycarboxylic acid ferric complex salt (1,3DPT
A-Fe, Sn [IT^, Pe, etc.] is usually preferably used in the form of an alkali metal salt or an ammonium salt, and ammonium salts are particularly preferred because of their excellent solubility and bleaching power. Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex salt may contain a metal ion complex salt other than iron, such as cobalt or copper.

Further, in addition to the above-mentioned ferric aminopolycarboxylic acid complex salt, it is preferable to add to the bleaching solution of the present invention a 7-minobolycarboxylic acid such as ethylenediaminetetraacetic acid, or an alkali metal salt or ammonium salt thereof. In particular, it is preferable to add the same type of aminopolycarboxylic acid as the compound used as the bleaching agent. The preferred amount of these aminopolycarboxylic acids to be added is o. ooot mol/i to 0.1 mol/l, more preferably 0.003 to 0.05 mol/l
It is. Various bleaching accelerators can be added to the bleaching solution of the present invention. Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
, No. 812, British Patent No. 1,138,842, Japanese Patent Application Publication No. 1%53-95630, Research
Compounds having a mercabuto group or disulfide group described in Disclosure No. 17129 (July 1978 issue), thiazolidine derivatives described in JP-A-50-140129, and U.S. Patent No. 3,706.561 The thiourea derivatives described, the iodides described in JP-A-58-16235, German Patent No. 2.748,430
Polyethylene oxides described in the specification of the Japanese Patent Publication No. 4
Polyamine compounds described in Japanese Patent No. 5-8836 can be used. Particularly preferably British Patent Nos. 1 and 1
Mercabut compounds such as those described in No. 38.842 are preferred. The bleaching solution of the present invention preferably contains bromine ions as a rehalogenating agent. The preferred amount of bromide ion added is 1.2 mol/l or more, particularly 1.5 to 2 mol/l.
．． 0 mol/i is preferred.

Furthermore, the bleaching solution may contain chloride ions and iodide ions in addition to the above-mentioned bromine ions. These halogen ions can be added as alkali metal salts or ammonium salts, but it is particularly preferable to add them as ammonium salts. In addition, nitrates such as ammonium phosphate and sodium phosphate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid. an inorganic acid of the Ifl class or higher having pHffl binding ability,
Known additives that can be commonly used in bleaching solutions, such as organic acids and their salts, and metal corrosion inhibitors such as ammonium sulfate, can be added. It is preferable to aerate the bleaching solution in order to oxidize the ferrous iron complex produced by the reaction with the color developing solution brought in by the bleaching process or the photosensitive material. Aeration may be performed only during processing, only while adjusting the temperature of the automatic processor, or throughout the day, but it is better to perform it as thoroughly as possible. In the present invention, after processing with a bleaching solution, processing is performed with a processing bath having fixing ability. Immediately after treatment with a bleaching solution, treatment with a treatment bath having fixing ability is preferred because the effects of the present invention are most clearly exhibited. After processing with a bleaching solution, washing with water, etc., and then processing with a processing bath that has fixing ability increases the number of steps by one, and it is not preferable from the viewpoint of processing speed and compactness of the processing machine. However, this may be done in order to assist the effects of the present invention.

The processing bath having fixing ability according to the present invention refers to a bleach-fixing bath and a fixing bath. As fixing agents for processing solutions used in processing baths having these fixing abilities, thiosulfates (e.g., sodium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate), thiocyanates (e.g., sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate)
, thioether compounds, thioureas, large amounts of iodide salts, etc., but it is preferable to use thiosulfate because it provides a high fixing speed and exhibits the effects of the present invention most markedly. Ammonium thiosulfate is particularly preferred in terms of solubility and fixing speed. It is also good to use it together with other fixatives. The amount of these fixing agents is preferably 1.1 mol/l or more, particularly preferably 1.3 to 1.7 mol/l. Within the preferred range, the effects of the present invention are significant. When the bath having the fixing ability of the present invention is a bleach-fixing bath, it may contain a known bleaching agent in addition to the above-mentioned bleaching agent. The fixing bath of the present invention contains preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, bisulfites of aldehyde compounds (e.g., acetaldehyde, sodium bisulfite, etc.), and preservatives. etc.) or carbonyl bisulfite adducts, sulfinic acid compounds, etc. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained. Especially as a preservative,
Sulfinic acid compounds described in JP-A-62-143048 can be used. The bath having fixing ability of the present invention contains 1,3-DPTA-Fe by bringing in the bleaching solution of the pre-bath with the photosensitive material, but in this case, the stability of the processing solution having fixing ability is slightly reduced. There is a tendency to In order to improve the stability of a processing solution having fixing ability, it is preferable to add an aminopolycarboxylic acid chelating agent or a phosphonic acid chelating agent. As the organic phosphonic acid chelating agent, the following general formula (1), (
Examples include compounds represented by 2) or (3).

General formula (1) 0H MxO3P-C-POxM2 R General formula (2) General formula (3) In the formula, M represents a hydrogen atom, lithium, sodium, potassium, or ammonium, and is preferably a hydrogen atom. Further, R represents an alkyl group or alkenyl group having 1 to 6 carbon atoms, and R2 represents a 7-rukylene group having 2 to 8 carbon atoms. These substituents may be linear or branched.
The preferred carbon numbers of RI and Rt are 1-3 and 2-6, respectively. a, b, c, d, e, r and g are each an integer of 1 to 3, preferably 1. Specific examples include 1-hydroxyethylidene-131 diphosphonic acid, 1-hydroxybutylidene-1. 1-
Diphosphonic acid, N,N,N',N'-monoethylenediaminetetraphosphonic acid, N,N,N',N'-brobylenediaminetetraphosphonic acid, N,N,N',N''-hexylenediaminetetraphosphonic acid Acid, N, N, N', N'-
Butylene diamine tetraphosphonic acid, N,N,N-nitrilotrimethylenephosphonic acid and N,N,N-nitrilotribrobylenephosphonic acid or salts thereof (e.g.
ammonium and sodium salts). The amount of the chelating agent added to the processing liquid having fixing ability is 0.
01 mol/I! ．． or more, particularly preferably 0.0
A content of 2 to 0.1 mol/min is preferable because it can dramatically improve the stability of a processing solution having fixing ability.

In particular, the effect is great when processing with a fixing solution immediately after processing with a bleaching solution containing 1.3-DP-A-Fe.

Particularly preferred chelating agents include organic phosphonic acid-based chelating agents. Among them, 1-hydrocychetylidene-1 small diphosphonic acid or a salt thereof (
For example, ammonium or sodium salts) are most preferred.

The pH of the processing liquid having the fixing ability of the present invention is 3 to 9, preferably 5 to 8.

The shorter the total time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes.

The treatment temperature is 25°C to 50°C, preferably 35°C to 45°C. Preferred temperature W! In the box,
The Mm speed is improved and the occurrence of streaks after processing is effectively prevented. In the grudge removal process of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention. A specific method for strengthening stirring is disclosed in JP-A-62-18346.
No. 0, No. 62-183461, a method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, and JP-A-6218
A method of increasing the stirring effect using the rotating means of No. 3461,
Furthermore, there is a method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface, and a method of improving the stirring effect of the entire processing liquid.
One method is to increase the amount of reflux. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is thought that improved agitation speeds up the supply of bleach and fixing agent into the emulsion film, thereby increasing the speed of degreasing. The agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator. The cross-over time from each processing solution to the next processing solution (the time in the air from when the photosensitive material leaves the processing solution to when it enters the next processing solution) of the present invention is preferably within 10 seconds, more preferably 5 seconds or less. Within seconds.

The automatic developing machine used in the present invention is disclosed in Japanese Patent Application Laid-Open No. 601912.
No. 57, No. 60-191258, No. 60-19125
It is preferable to have the photosensitive material conveying means described in No. 9. As described in JP-A No. 60-191257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The color developing solution of the present invention will be explained below.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are P-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. D-IN. N-diethyl-P-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5-(N-ethyl-N-laurylamino)toluene D-4 4-(N-ethyl-N-(β-hydroxy ethyl)amino]aniline D-5 2-Methyl-4-[N-ethyl-N-[β-hydroxyethyl)amino]aniline D-6 4-amino-3-methyl-N-ethyl-N-(
β-(methanesulfonamido)ethyl)aniline D-7 N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N,N-dimethyl-P-phenylenediamine D-9 4-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N
-β-ethoxyethylaniline D-11 4-amino-3-methyl-N~ethylN-
β-Butoxyshetylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Moreover, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per 1 liter of developer solution.
More preferably a concentration of about 0.5g to 1og.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

However, in order to improve the color development properties of color developing solutions, it is preferable to reduce sulfite ions as much as possible. A preferable amount of preservative added is 0.00000000000000000000000000000000000000000000000000000000 that type that type that per color developer that is added;
5 g to 10 g, more preferably 1 g to 5 g, and in addition to sulfite, various hydroxylamines, JP-A-63-43 are used as compounds that directly preserve the color developing agent.
Hydroxamic acids described in No. 138, No. 63-14604
Hydrazines and hydrazides described in No. 1 and No. 63-170642, No. 63-44657 and No. 63-58
It is preferable to add the phenols described in No. 443, the α-hydroxyketones and α-aminoketones described in No. 63-44656, and/or the various saccharides described in No. 63-36244. In addition, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254, JP-A-63
-21647, 63-146040, 63-2
Monoamines described in No. 7841 and No. 63-25654, etc., diamines described in No. 63-30845, No. 63146040, No. 63-43139, etc., No. 63
-21647 and polyamines described in 63-26655, polyamines described in 63-44655, nitroxy radicals described in 63-53551, 6
It is preferable to use the alcohols described in No. 3-43140 and No. 63-53549, the oximes described in No. 63-56654, and the tertiary amines described in No. 63-239447. As other preservatives, JP-A-57
-44] various metals described in 48 and 57-53749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, JP-A-56-94349 The polyethyleneimine described in i12, the aromatic polyhyde compound described in U.S. Pat. No. 3,746,544, and the like may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroquine compound.

The color developer used in the present invention preferably has p}1
9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pK, it is preferable to use various types of mild punishment. Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
and sodium droxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/l.
It is preferable that it is more than 0.1 mol/2 to 0.1 mol/2.
Particularly preferred is 4 mol/2. In addition to sono, various calcium chloride agents can be used in the color developer as an anti-settling agent for calcium and magnesium, or to improve the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as aminopolycarboxylic acid compounds described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347,
Special Publication No. 56-39359 and West German Patent No. 2, 227
, organic phosphonic acids described in No. 639, JP-A-52-1
No. 02726, No. 53-42730, No. 54-121
No. 127, No. 55-126241 and No. 55-6
Phosphonocarbon 9M described in No. 59506, etc., and other JP-A-58-195845, JP-A No. 58-20344
Examples include compounds described in No. 0 and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, jethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',Il'~tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1. 2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1.2.
4- }Ricarboxylic acid, 1-hydrocychetylidene-1
．． 1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N''-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.18 to Log per hit. Color developer has
Any development accelerator can be added if necessary.
However, it is preferable that the color developer of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, formulation properties, and prevention of color staining. Here, "practically" means that the developer contains less than 2 d per 11 d of the developer, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826,
44-1.2380, 45-9019, and U.S. Pat. No. 3.813.247, etc.;
p-phenylenediamine compounds represented by No. 5554, JP-A-50-137726, JP-B No. 443007
No. 4, JP-A-56-156826 and JP-A No. 52-434
Quaternary ammonium salts represented by No. 29, etc., U.S. Patent No. 2,494,903, Japanese Patent Publication No. 11431/1983,
U.S. Patent Nos. 2,482,546 and 2,596,
Amine compounds described in Japanese Patent Publications No. 37-16088 and Japanese Patent Publication No. 42-252, etc.
No. 01, U.S. Patent No. 3,128.183, Special Publication No. 1973
-11431, 42-23883, and U.S. Patent No. 3,532.501, and other 1-phenyl-3-virazolidones,
Imidazole, etc. can be added as necessary. In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of spinal antifoggants include penzotriazole, 6
-Nitropenzimidazole, 5-nitroisoindazole, 5-methylbenzutriazole, 5-nitropenzotriazole, 5-chlorobenzotriazole, 2
Typical examples include nitrogen-containing heterocyclic compounds such as -thiazurylpenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain an optical brightener. As the optical brightener, 44°-diamino-2,2°-disulfostilbene compounds are preferred.

The amount added is O~5g/ρ, preferably 0. 1g~4g/
It is 12. Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, alkylphosphonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. It is preferable that the amount of replenishment is small, but it is 100 to 1500 d per irrr of photosensitive material.
, preferably 100 to 800 m. More preferably, it is 100-400 ml. Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment. The processing method of the present invention can also be used for color reversal processing. In the present invention, the black-and-white developer used at this time can be a so-called black-and-white first developer used in the reversal processing of color photographic light-sensitive materials, which is commonly known, or a developer used in the processing of black-and-white light-sensitive materials. Also, the carrier can contain various well-known additives that are added to black and white developers.

Typical additives include developing agents such as 1-phenyl-3-virazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Development inhibitors consisting of potassium bromide, inorganic or organic inhibitors such as 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and amounts of iodides and mercapto compounds. The processing method of the present invention includes processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after a treatment step that has a fixing ability, it is common practice to perform treatment steps such as water washing and stabilization, but after a bath that has a fixing ability, stabilization is performed without actually washing with water. You can also use a simple processing method. The rinsing water used in the rinsing process may contain known additives as necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
A fungicide and anti-mold agent that prevents the growth of various bacteria and algae (
For example, isothiazolones, organic chlorine disinfectants, penzotriazole, etc.), surfactants to prevent drying load and unevenness, etc. can be used. Or L. E.
West'Water Quality Criter
ia”, Photo. Sci. andBng. .
vol. 9, No. 6. pages344-35
9 (1965) etc. can also be used. As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and AI, optical brighteners, chelating agents (e.g. 1-hydroxyethylidene-1.1 diphosphonic acid), bactericides, and antifungal agents as necessary. , a hardening agent, a surfactant, etc. can be used. Here, formalin can also be removed from the stabilizing solution. In this case, reduction of environmental pollution (reduction of pollution load)
, which is preferable in terms of improving the working environment.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages.

The replenishment amount is 1 to 5 of the amount brought in from the previous bath per unit area.
0 times, preferably 2 to 30 times, more preferably 2 to 15 times
It's double.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to a SMg concentration of 51 llg/l or less, water that has been sterilized with halogen, ultraviolet germicidal lamps, etc. In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to compensate for such concentration of the processing solution, it is preferable to replenish an appropriate amount of water or correction solution. Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability. Incidentally, the amount of developing agent remaining in the film of the photosensitive material after processing can be determined according to the method described in Japanese Patent Publication No. 63-23529. In other words, after developing an unexposed sample, there are 8! ! The developing agent extracted with a solvent (e.g. ethyl acetate) is added to a solution consisting of a dispersion containing the cyan coupler described below and an aqueous red blood salt solution, and the concentration of the cyan dye formed is measured and quantified by an absorbance method. Can be done. The light-sensitive material of the present invention only needs to have at least one layer each of a blue-sensitive layer, a green-sensitive layer, and a halogenated daughter emulsion layer of a red-sensitive layer on a support. There are no particular limitations on the number and order of the emulsion layers and non-photosensitive layers. As a typical example, a blue-sensitive, green-sensitive and red-sensitive photosensitive layer consisting of a plurality of silver halide milk 7FII layers having substantially the same color sensitivity but different photosensitivity is formed on a support. It is a silver halide photographic light-sensitive material having the following structure, and generally the unit photosensitive layers are arranged in the order of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer from the support side.

However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-bad light layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-1.13440, No. 61-2
Coupler, DIR compound, etc. as described in No. 0037 and No. 61-20038 may be included, and a color mixing inhibitor as commonly used may be included.

The plurality of halogenated emulsion layers constituting each unit photosensitive layer include a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure is preferred and can be used.
Generally, it is preferable to arrange the halogen emulsion layers so that the luminous intensity decreases in order toward the support, and a non-irradiating layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-temperature emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support. As a specific example, from the side farthest from the support: low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (Gl1) / low-sensitivity green-sensitive layer (GL) )/
High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (RL)
), or BH/BL/GL/GH/RH/RL, or BH/BL/Gll/GL/RL/RH, etc. Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/I
? They can also be arranged in the order of II/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/Rl+ can be arranged in this order from the farthest side from the support. ．． In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer with a low density is disposed and is composed of 3Ns having different photosensitivity, the photosensitivity of which is sequentially lowered toward the support. Even in the case where the layer is composed of three layers having different photolucidities, as described in JP-A No. 59-202464, a medium-sensitivity emulsion is added from the side remote from the support in the same color-sensitive layer. They may be arranged in the following order: layer/high sensitivity emulsion layer/low sensitivity emulsion layer.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, the layers may be arranged in the following order: low-speed emulsion layer/medium-sensitivity emulsion layer/high-speed emulsion layer.

Also, in the case of four or more layers, the arrangement may be changed as described above. To improve color reproduction, U.S. Patent No. 4.663,2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
It is preferable to arrange a multilayer effect donor layer (CL) having a different spectral luminance distribution from the main photosensitive layer such as BL, GL, RL, etc., as described in the specification of No. 580, adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. ．． Particularly preferred are silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide. Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may also be a type with crystal defects, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 or less, or large grains with a projected area diameter of about 1 OuTB, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No. 17643
(December 1978), pp. 22-23, 'I. Emulsion preparation and
types)'', and Nfl 1B716 (1
(November 979), 648 pages, "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.GIafk)
ldes, Chemic et Physique
Photograph-ique, Paul Mon
tel+ 1967), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (G.F. DuffinPho)
tographic En+ulsion Chemi
stry (Focal Press, 1966)),
“Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (ν. L, Zelikmanet al.
．． ．． Making and Coating Pho
tographic Emul-sion, Foca
1 Press+ 1964). U.S. Patent Nos. 3,574,628 and 3,655,39
Also preferred are the monodispersed papules described in eg No. 4 and British Patent No. 1,413,748.

Further, tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970): U.S. Patent No. 4
．． 434.226, 4,414.310, 4,
433,048, 4,439,520, and British Patent No. 2,112,157. The crystal structure may be uniform, the inside and outside may have different halogen compositions, it may have a layered structure, or silver halides of different compositions may be bonded together by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as Rodan oxide or lead oxide. Silver halide emulsions which may contain a mixture of grains of various crystal forms are usually used which have been subjected to physical ripening, chemical ripening and spectral enhancement. Additives used in such processes are Research Disclosure Ni1
17643 and Doshu 18716,
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Mulberry plate fan and 11D17643 Decoy'l group 1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 23~
Page 24 Page 648 Right column - Super sensitizer 6
Page 49 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Stain inhibitor Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27 Page 650, right column 12 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same as above Inhibitor Also, deterioration of photographic performance due to formaldehyde gas In order to prevent
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503. Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-C-C. As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1.425.020, British Patent No. L. 476,760
No. 3,973,968, U.S. Patent No. 431
No. 4.023, No. 4.51L649, European Patent No. 2
No. 49473A, etc. are preferred.

As the magenta coupler, 5-virazolone-based and virazoloazole-based compounds are preferred, and US Pat.
No. 0,619, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432
No. 3,725, 067, Research Disclosure Nα24220 (June 1984), JP-A-60-33552, Research Disclosure Nα24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573
No. 0, No. 55-118034, No. 60-185951
No. 4,500. No. 630, No. 4,540
, No. 654, No. 4,556.630, International Publication W○
Particularly preferred are those described in No. 88/04795. Cyan couplers include phenolic and naphthol based couplers, and are disclosed in U.S. Pat. No. 4.052, 21.
No. 2, No. 4,146.396, No. 4,228,2
No. 33, No. 4,296,200, No. 2,369,
929, 2.801, 171, 2.77
2, 162, 2,895.826, 3,
No. 772,002, No. 3,758,308, No. 4
, 334.011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,
No. 365A, No. 249,453A, and U.S. Patent No. 3.
No. 446,622, No. 4.333,999, No. 4
, 775.616, 4,451,559, 4,427.767, 4,690,889, 4,254,212, 4,296. Preferably, those described in No. 199, JP-A-61-42658, etc. Colored couplers to correct unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
Section 1G, U.S. Patent No. 4.1.63.670, Japanese Patent Publication No. 5
No. 7-39413, U.S. Patent No. 4,004,929,
British Patent No. 4,138,258, British Patent No. 1,146,3
The one described in No. 68 is preferred. Also, U.S. Patent No. 4,
No. 774.181, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, or a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
4.576910, British Patent No. 2, 102.
It is described in No. 173, etc. Couplers that release photographically useful residues upon cambling can also be preferably used in the present invention. A DIR coupler that releases a development inhibitor is the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferably, those described in U.S. Pat. No. 63-37346, U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097,140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include the competitive couplers described in U.S. Pat. No. 4.130.427, U.S. Pat. , multi-equivalent couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler release power pullers,
DIR coupler redox compound or DTRL
, Donx-releasing redox compound, European Patent No. 1733
02A, which emits a dye that recolors after separation, R. D. Na 11449, Na 2424 1, bleaching accelerator releasable power blur described in JP-A-61-201247, etc., ligand-releasing power puller described in U.S. Pat. No. 4,553,477, etc., JP-A-63-75747 Leuco dye-releasing couplers described in U.S. Pat. No. 4,774
．． Examples include couplers that emit fluorescent dyes as described in No. 181. The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods. Examples of high-boiling point solvents other than the high-boiling point organic solvents of the present invention used in the oil-in-water dispersion method are described in U.S. Patent No. 2. It is described in No. 322027, etc. Further, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C or higher and about 160°C.
The following organic solvents can be used, and typical examples include ethyl acetate, butyl acetate, ethyl blobionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Pat. It is described in No. 230, etc.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248 and JP-A-1
1,2-penzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, as described in No.-80941;
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)penzimidazole. ? The invention can be applied to various color photosensitive materials. Color negative film for general use or motion pictures;
Typical examples include color reversal films for IDs and televisions. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nil 17643, and Nil (1
18716, from the right column on page 647 to the left column on page 648. In the optical material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 28 or less, and 2.
34 or less is more preferable<, 20n or less is even more preferable.
Further, the membrane swelling rate Tl/t is preferably 30 seconds or less,
More preferably 20 seconds or less. The film thickness is 25℃ relative humidity 5
It means the film thickness measured under 5% humidity control (2 days), and the film swelling rate TI/■ can be measured according to a method known in the art. For example, A Green (A
, Green) et al., published by Photography Inc. Science and Engineering (Photogr.
SCi. Eng. ). Volume 19. No. 2, 124 ~1
Are you using the swell meter (swelling meter) of the type described on page 29?
T+/t can be measured by using a color developer.
'C, 90% of the maximum swollen film thickness reached when treated for 3 minutes and 15 seconds is defined as the saturated film thickness, and the time required to reach the film thickness of T,/1 is defined as the saturated film thickness.

The membrane swelling rate TI, (2) can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions of the coating solution. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described earlier using the formula: (maximum swollen film thickness - film thickness)/film thickness. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
and Schiff base-type compounds described in No. 15 and No. 159,
Aldol compounds described in U.S. Patent No. 13,924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 135628. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
It may also contain vilapridone. Typical compounds are described in JP-A Nos. 56-64339, 57-144547, and 58-115438. (Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these. Example 1 On a subbed cellulose triacetate film support,
Sample I, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the angry light layer) The coating amount is silver halide and colloidal silver in g/g of silver.
The amount expressed in rrf units is expressed in g/rrf units for organic materials such as gelatin and covlar oil, but the amount expressed in moles per 1 mole of silver halide in the same layer for sensitizing dyes. .

The numbers in parentheses at the end of each layer indicate the dry film thickness (unit: 4L 1st layer: anti-halation M black colloidal silver silver coating amount 0.20 gelatin 2.15UV-1
0.10UV-20・20 C p d - 1 0.
05Solv-1 0.01
Solv-2 0.01So
lv-3 0.08 (2.1
) 2nd layer: Intermediate layer fine particle bromide 1! (Equivalent sphere diameter 0.07n)
O. 15 Gelatin 1.00Cpd
-2 0.20 (1.0) Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (8g1 10.0 mol%, internal high Agl
Type, equivalent sphere diameter 0.7-, coefficient of variation of equivalent sphere diameter 14%, 1
Tedecahedral grains) Coating amount: 0.50 silver iodobromide emulsion (Agl 4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 m, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral grains) Amount 0.40 gelatin
2. OoEx S-1
4.5XlO-'E x S-
2 1.5X10-'Ex
S-3 0.4X10-'
Ex S-4 o. 3x
to-'Ex C-1
0.33E x C-2
0.0092 x C-3
0.023ExC-6
0.14 (2.3) 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Agl 16 mol%, internal high Agl type,
Equivalent sphere diameter 1.0-, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 4,0) Gelatin ExS-I EχS-2 ExS-3 ExS-4 ExC-3 ExC-4 ExC- 6 Silver coating amount 0.80 1.30 3X10-'lx10-'0.3X10-'0.3X10-' 0.10 0.08 (1.5) 5th layer: 3rd red-sensitive emulsion layer Silver bromide emulsion (Agl 10.0 mol%, internal high Agl
Type, equivalent sphere diameter 1.2-, coefficient of variation of equivalent sphere diameter 28%,,
Plate-shaped particles, diameter/ff ratio 6.0) Silver coating amount 1. IO Gelatiso l620ExS
-1 2X10-'E x
S-2 0.6X10-
'E x S - 3 0.2
xlO-'E x C-4
0.07E x C-5
0.06Salv-1
0.24 (1.
6) 6th layer: Intermediate layer gelatin 1,30Cpd
-4 0.10 (1.1) 7th layer: 1st green bad emulsion layer iodobromide iff emulsion (Agl 10.0 mol%, internal height A
gI type, equivalent sphere diameter 0.7-, coefficient of variation of equivalent sphere diameter 14%
, tetradecahedral grains) Daughter coating amount 0.20 Silver iodobromide emulsion (^fi+ 4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4-, coefficient of variation of equivalent sphere diameter 22%, 14
Face piece particles) Silver coating amount 0.10 gelatin
1.40ExS-5
5xlO-'ExS-6
2X10'''ExS-7
1XIO-'ExM-1
0.41ExM-2
0.10E x M-5
0.03 So
lv-1 0.
20 (1.9) 8th layer: second green emulsion layer silver iodobromide emulsion (Agl 10 mol%, internal high eight gl type,
Equivalent ball diameter 1.0. , coefficient of variation of equivalent sphere diameter 25%, temporary particles, diameter/thickness ratio 3,0) Silver coating amount 0,50 Gelatin 0.45E x
S-5 3.5X10-'E
x S-6 1.4X
10-'Ex S-7
0.7xlO-'E x M-1
0.09ExM-3
0.01Solv-1
0.15 (0.8) 9th layer: Intermediate layer gelatin 0.50 (0.4) 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (Agl 10.0 mol%, internal high Agl
Type, equivalent sphere diameter 1.2. , coefficient of variation of equivalent spherical diameter 28%, plate-like particles, diameter/thickness ratio 6.0) Coating 1 1.20 Gelatin 1.40E x
S-5 2X10-'
E x S-6 0.8x
lO-'Ex S-7
0.8X10-'E x M-3
0.01ExM-4
0.14ExM-1
0.04E x C-4
0.005Solv-1
0.2 (1.8) 11th N: Yellow filter layer C p d - 3 0
．． 05 Gelatin 0.50S
olv-1 0.10 (0.5
) 12th layer: Intermediate layer gelatin 0.50Cpd-
2 0.10 (0.5) 13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (All 10 mol%, internal high Agl type,
Silver coated i1 0.15 silver iodobromide emulsion (Agl 4.0 mol%, internal high Agl type, equivalent sphere diameter 0.7 mol%, equivalent sphere diameter 0.7 pcs, coefficient of variation of equivalent spherical diameter 14%, tetradecahedral grains). 4n, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particle)! ! Application l O. 08 gelatin
1.20ExS-8
3X10-'E x Y-1
0.62E x Y-2
0.02Solv-1
0.40 (1.9) 14th layer: 2nd blue emulsion layer silver iodobromide emulsion (8 gl 19.0 mol%, internal high Agl
Type, equivalent sphere diameter LOs, coefficient of variation of equivalent sphere diameter 16%, 14
Gelatin ExS-8 EXY-I Solv-1 15th layer: Intermediate layer silver coating amount 0.30 0.30 2X10-' 0.22 0.07 (0.7) Fine grain silver iodobromide (All 12 Mol%, uniform type, equivalent sphere diameter 0.13-) i! Coating amount: 0.20 gelatin. ．． 36 (0.4) 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 14,0 mol%, internal high Agl
Mold, equivalent sphere diameter 1.5-, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5.0) Coated silver amount l, 20 Gelatin 0.90E x
S-8 t. sxio
-'ExY-1. 0.
20Solv-1 0.07
17th N: 1st protective layer gelatin [JV-I LIV-2 Solv Solv I 18th layer: 2nd protective layer Fine grain silver bromide (equivalent sphere diameter 0.07) Silver coating amount Gelatin polymethyl methacrylate particles (diameter 1 .5 m) W-1 H-1 Cpd-5 (1.3) 1.80 0.10 0.20 0.01 0.0] (1.7) 0.1B 1.05 0.20 0. 02 0,40 (2.1) UV-1 ExC-3 0H UV-2 ExM-3 ExC-2 ExC-4 0H ExC Cth HtS ExM-4 Cl ExM-5 ExM 1 CI+. ExM-2 ExY-1 ExY ExS CX}I5 ExS-2 CJs ExS-3 CtHS ExS-8 ExS-1 Solv-1 Solv ExS C.I1, ExS-5 CtllS Solv-3 cpa-t Cpd-2 0■ Cpd-3 ?C{1 ■ Cpd Call.(n) CJ+ 1(n) cpd-5 w-1 CJl?SOxNHCH*CHzCHzOCHzCHt
N'<CHJ 3H-1 CHt -CHSO! CH! CONH-CI! I CHt =CHSOtCHzCONH-CIltNext, the layer structure, the compound used in each layer and its coating amount, the emulsion type and its coating amount are the same as Sample I without changing Sample 1.
The coating amounts of N and the second layer were changed for each layer, and the hardening agent 11-1 was added in the same ratio as Sample F41 to the total amount of gelatin, and the coating amount of the first and second layers was changed as shown in Table 1. A sample in which the total thickness of nta was changed, and a sample in which the oil used for the red beading layer (3rd N, 4th N, and 5th layer) was changed as shown in Table 1, and the same coating amount as in sample 1 was added. 2 to 15 were produced.

These prepared samples 1 to 15 were cut and processed into a width of 35 mm, exposed to sunlight (color temperature of the light source 4800'K), and processed using the processing method 1 shown below. Furthermore, as a comparative treatment, the following treatment method 2 was performed in the same manner as treatment method 1. Processing method 2 is a process in which the bleaching effect after the process can be considered to be virtually zero. Buddha' uL1: Color development 3 minutes 15 seconds bleaching 40 seconds fixing 1 minute 30 seconds washing (13 30 seconds washing (2) 30 seconds stabilization 30 seconds drying 1 minute 00 seconds 37.8°C 38. 0°C 38.O'C 38,0°C 38.0'C 38,0°C 55°C The composition of the treatment liquid is shown below.

(Color developer) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate ■ (Unit: 2 g) 1.0 3.0 4,0 30.0 1.4 1. 5mg 2.4 Add 4-(N-ethyl-N-β-hydroxyethylamine)-2-methylaniline sulfate to pH (bleach solution) 1.3-Diaminopropanetetraacetic acid ferric ammonium hydrate 1.3 -Diaminopropanetetraacetic acid ammonium bromide ammonium nitrate acetic acid (98%) Add water to ρI [adjusted with aqueous ammonia (27χ)] (fixing solution) Ethylenediaminetetraacetic acid ammonium salt ammonium sulfite ammonium thiosulfate aqueous solution (700 g/1) 4. 5 1. Of 10.05 (unit 2 g) 144.0 2,8 84,0 20. O iii. o 1. O N 4.0 (Unit: 2g) 1.7 14.0 340.0m Add water ・ 1.02p1
{7.0 (Washing water) Tap water was mixed with 11 type strong acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and 011
Strongly basic anion exchange resin (Amberlite IRA)
-400) was passed through a mixed bed column packed with calcium and magnesium ion concentrations of 3 mg/F! followed by 20 m sodium isocyanurate dichloride
g/l and 15 hg/1 sodium sulfate were added. The pi of this liquid was in the range of 6.5 to 7.5.

(Stabilizing solution) (Unit: 2 g) Formalin (37%) 1. 2
ml surfactant 0.4
Add ethylene glycol water to ρH 1.0 1.02 5.0 to 7.0 JLr method 1 In the processing method 1, between the color developing bath and the bleaching bath, 1%
A treatment method that was exactly the same as treatment method 1, except for adding 2 minutes to the acetic acid aqueous solution bath. These treated samples obtained by treatment methods 1 and 2 are referred to as group A and group R, respectively. The concentrations of these samples were measured, and the Dain measured at the green light density was read from the obtained characteristic curve. The evaluation was based on the Dmin of the R group sample and was calculated according to Table 2. The results are shown in Table 2. From the results in Table 2, the total thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer of the support, which satisfies the constituent elements of the photosensitive material of the present invention, is 2.5%. The photosensitive materials (Samples 7 to 15) in which the dielectric constant is 1 or less and a high boiling point organic solvent with a dielectric constant of 6.0 or less is used in the red-sensitive layer are excellent with a small Dmin. Compared to this, Comparative Samples 1 to 6 have higher Dmin and are clearly inferior.

That is, Comparative Sample 6 has the same oil as Sample 7 of the present invention, but the film thickness of the first layer and the second layer exceeds 2,5-, and as a result, Dmin is significantly higher. It has become. Furthermore, when Comparative Sample 2 and Samples 7, 11 to 15 of the present invention are compared, the film thickness of the first layer layer 2N is the same, but the oil used in the red sensitive layer is different from that of Samples 7, 11 to 15. Sample 15 has a dielectric constant of 6.0 or less, and Sample 2 has a dielectric constant of 6.01! This is what is being learned. Therefore, the sample of the present invention is superior, but the comparative sample fl42 has clearly high DTain (inferior). Furthermore, when looking at Comparative Samples 1 to 5, since oil with a dielectric constant greater than 6.0 is used in the red light layer, the first
Even if the thickness of the second layer was made smaller, a significant reduction in Dmin could not be achieved.

Example 2 The pH of the bleaching solution of treatment method 1 used in Example 1 was set to 3.7.
, 4.0, 4.5, 5.0, 5.5, and 6.0 were separately prepared with ammonia water, and treatment method 1 was used.
I created a bleaching solution that was exactly the same as the one above.

Except for using these bleaching solutions, the other treatment solutions and treatment steps were the same as those for Group A, and the sample 7 prepared in Example 1 was treated. The concentration of the treated sample was measured. From the obtained characteristic curve, read Dmin measured at green light density, and process method 2.
The bleaching strength was evaluated based on the difference from D@tn of sample 7 (sample 7 of group R) treated with .

The results are shown in Table 3.

Each of the bleaching solutions shown in Table 3 was prepared. Sample 7 prepared in Example 1 was treated in the same manner as in Group A for other treatment solutions and treatment steps. The density of the treated sample was measured, and the Dmin measured at the green light density was read from the obtained characteristic curve, and the difference from the Dmin of sample 7 (sample 7 of group R) treated with processing method 2 was calculated to determine the bleaching fog. was evaluated.

From the results in Table 3, it can be seen that when the pl+ of the bleach solution exceeds 5.0, the level of bleaching power increases significantly. That is, when processing using the photosensitive material of the present invention, the pl+ of the bleaching solution is preferably 5.0 or less. Even more preferably p
H4. It is less than or equal to 0. When the photoreceptive material of the present invention is treated with the pH of the bleaching solution set to 4.0 or less, the bleaching strength is at a level that is virtually no problem.

Example 3 In the treatment method 1 of Example 1, the acetic acid concentration of the bleach solution was increased to 4
0g/1, 55g/l, 60g#, 80g#! , 11
0g#! , 220 g/1, and the other conditions were the same as those of treatment method 1. The results are shown in Table 4.

Table 4 As is clear from Table 4, the acetic acid concentration in the bleaching solution is 1.0.
If it is less than mol/l, the level of bleaching power deteriorates significantly. Further, when the concentration is 1.0 mol/l or more, the bleaching power is at a level where there is virtually no problem when processing the photosensitive material of the present invention. Therefore, the acetic acid concentration in the bleach solution is preferably 1.0 mol/2 or more. Example 4 The oxidizing agent (1,3-diaminopropanetetraacetic acid ferric ammonium hydrate) and chelating agent (1,3-diaminopropanetetraacetic acid) of the bleach solution used in the example process are shown in Table 5. A bleaching solution was prepared by replacing the oxidizing agent and chelating agent shown in the same number of moles. Using this bleaching solution, the bleaching time was set to 35 seconds, and the other conditions were exactly the same as those in Processing Method 1 of Example 1, and Example 1 (7) tK material 7 was processed to remove the residual silver in these samples. The amount was determined by fluorescent X-ray method. The results are shown in Table 6. The evaluation method in Table 6 was expressed as the difference (ΔD) between D*in measured under green light after storage under the above conditions and Dm:n measured under green light under the above conditions before the start of the test. ΔD in = (D in after test) - (D in in before test) The results are summarized in Table 7. As is clear from Table 6, the redox potential of the oxidizing agent in the bleaching solution is within the range of the present invention, 0. Oxidizing agents with a voltage of 15 V or higher have excellent derooting properties. On the other hand, 0.
If the oxidizing agent is smaller than 15 V, the amount of residual silver will be extremely large, which is not preferable. Example 5 Samples 1 to 15 prepared in Example 1 were treated at the pH level of Example 2.
Processing method 1 using bleaching solutions of 4.0, 5.0 and 6.0
Processed with. The obtained samples were stored under the following conditions and the increase in stain in the unexposed areas was evaluated. Dark and humid heat storage stability: 60'C, 70% RH, 10 days From Table 7, Samples 7 to 15, which are photosensitive materials that meet the constituent requirements of the present invention and were processed with a bleaching solution having a ρ■ of 5.0 or less, are It can be seen that the increase in stain in image storage after processing is clearly small.

Example 6 On a subbed cellulose triacetate film support,
Sample 21, which is a multilayer color light-sensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/%, and for silver halide, the coating amount is expressed in vA conversion. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer. The numbers in parentheses at the end of each layer indicate the dry film thickness (unit: 1)
．． (Sample 21) First layer (antihalation layer) Black colloidal silver j! 0.18
Gelatin 1.50 (1.2
) 2nd layer (middle N) 2,5-di-L-bentadecylhydroquinone EX-1 Snake X-3 EX-12 U-1 U-2 U-3 HBS-1 HBS-2 Gelatin No. 3N (first red Emulsion layer) Emulsion A Emulsion B Sensitizing dye I Sensitizing dye ■ Sensitizing dye m EX-2 0.18 0.07 0.02 0.002 0.06 0.08 0. l0 0.10 0.02 1.40 (1.7) i艮 0.25 言艮 0.25 6.9 X 10-S 1.8 X 10-' 3. lX10-' 0.335 EX-10 HBS-1 Gelatin 0.020 0.060 l. 20 (1.5) 47i! (Second red-sensitive emulsion N) Emulsion G Enhancing dye 1 Sensitizing dye U Enhancing dye ■ EX-2 EX-3 EX-10 HBS-1 Gelatin 1 1.0 5. I X10-'1.4x10-'2.3xlO-' 0.400 0.050 0.015 o. o6o 1.55 (2.0) 5th layer (3rd red-sensitive emulsion layer) Emulsion D Sensitizing dye I Sensitizing dye■ Enhanced dye■ Silver l. 60 5.4X10-5 1.4X10-'2.4xIO-' EX-3 EX-4 EX-2 8BS-L HBS-2 Gelatin 6th layer (middle layer) EX-5 8BS-1 Gelatin 7th layer (1st green emulsion layer) Emulsion A Emulsion B Sensitizing dye V Sensitizing dye ■ Enhancing dye ■ EX-6 EX-1 0.010 0. 080 0. 097 0.20 0.12 1.85 (2.4) 0.040 0. 020 1.15 (1.0) Silver 0. l5 Reiwa 0.15 3. OX10-' 1. OX10-'3.8X10-' 0.260 0.021 EX-7 EX-8} {BS-1 Gelatin 8th layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye■ Sensitization Dye ■ EX-6 EX-8 EX-7 HBS-1 Gelatin 9th layer (third green emulsion layer) Emulsion E Sensitizing dye ■ Sensitizing dye ■ 0.030 0.025 0.100 1.25 ( 1.5) Silver 0.45 2. IX10-'? ．． OX10-'2.6X10-' 0.094 0.018 0.026 0.160 0.70 (1.0) Silver 1.2 3.5X10-' 8. O Blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Enhancement dye ■ EX-9 3. OX10-' 0.015 o. ioo O. 025 0.25 0.10 1.75 (2.2) Silver 0.05 0.08 0.03 1.10 (1.0) Silver 0.08 Silver 0.07 Grudge 0.07 3.5XIO-' 0.721 EX-8 HBS-1 Gelatin 12N (second blue emulsion layer) Emulsion G Sensitizing dye EX-9 EX-to HBS-1 Gelatin 13th layer (third blue emulsion layer) Emulsion H Sensitizing dye ■ EX-9 HBS-1 Gelatin 0.042 0.28 1.25 (2.0) i 0.45 2. lXIO-' 0.154 0.00? 0.05 0.95 (Cl) Silver 0.77 2.2X10-' 0.20 0.07 0.90 (1.2) 14th layer (first protective layer) Emulsion ■ Silver 0.5 U-4 0, ]1 LJ-5 0. 17 HBS-1 0.05 Gelatin 1.30 (1.5) 15th layer (second protective layer) Polymethyl acrylate particles (approximately 1.5 m in diameter) 0.54 AS-1 0.20 Gelatin 1.25 ( 2.0) In addition to the above ingredients, gelatin hardener H-1 and a surfactant were added to each layer. EX- 1 EX-4 0H EX CthH+3(n) Shi! EX-2 EX-6 EX-3 I 0H EX Czlls EX-8 EX-11 EX-12 Shi! 2 EX-9 EX-10 U-1 U-2 U-3 U-4 0}1 Clh -Butyl phthalate sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ AS-1 H-1 ? Hz = CI1-501-CH■-CONII-CI
．． ? H. Engineering C11-So■-CH&-CON}I-CI
! , Sensitizing Dye■ Sensitizing Dye■ Sensitizing Dye■ Sensitizing Dye■ Sensitizing Dye■ Sensitizing Dye■ Sensitizing Dye■ Sensitizing Dye■
However, the coating amounts of the first and second layers were changed for each layer, and the hardening agent H-1 was added in the same ratio as Sample 21 to the total amount of gelatin, as shown in Table 8. 2nd N
A sample in which the total film thickness was changed, and a sample in which the oil used for the red beading layer (3rd layer, 4th N, and 5th layer) was changed as shown in Table 8, and the same coating amount as in sample 21 was added. 22-35
was created. These prepared samples 22 to 35 were cut and processed into 35 mm dl, and subjected to wenge exposure to sunlight (color temperature of the light source: 480 Q'K) and processed using processing methods 1 and 2 of Example 1. Table 8 These treated samples obtained by treatment methods 1 and 2 are designated as group B and group S, respectively. The density of these samples was measured, and from the obtained characteristic curve, D measured at green light density was
I read itn.

When the results were evaluated using the same evaluation method as in Example J, it was found that, as in Example I, sample 27 satisfied the structure of the present invention.
-35 had a lower Dmin than samples 21-26 and was clearly superior. Therefore, by using oil with a dielectric constant of 6.0 or less in the red-sensitive layer,
And by setting the film thickness of the first layer + second layer (all layers provided between the photosensitive layer closest to the support and the undercoat layer of the support) to 2.5 mm or less, bleaching fog can be greatly reduced. It is highly effective.

Example 7 The six types of bleaching solutions used in Example 2 (pl+ of 3.7, 4.
Sample 27 prepared in Example 6 was treated in the same manner as in Example 2 using bleaching solutions of 0, 4.5, 5, 0, 5.5, and 6.0. As in Example 2, the sample obtained here was evaluated and compared based on the difference in D+min from the S group sample, and it was found that the bleaching treatments of pl+ 5.5 and pll 6.0 resulted in a higher Dmin; In the treatment at pH 5.0 or lower, the height of DIIin was at a non-problematic level when a photoreceptor material (Sample 27) satisfying the constituent elements of the present invention was used. Therefore, in the bleaching treatment of the present invention, pll is 5.0
The following are preferred, and those with a pH of 4.0 or less are more preferred. Example Day Test #427 produced in Example 6 was used and treated with the same bleaching solution described in Example 3 with different concentrations of acetic acid.

The concentration of these samples was measured, Dmin was read from the obtained characteristic curve in the same manner as in Example 6, and the same evaluation as in Example 3 was performed. As in Example 3, the acetic acid concentration in the bleaching solution was When treated with a bleaching solution containing 1.0 mol/l or more, it was found that the bleaching strength was small, which was particularly excellent.

Example 9 Using sample 27 prepared in Example 6, the same treatment as in Example 4 was performed under the five treatment conditions used in Example 4, and the residual silver amount of each obtained sample was measured using fluorescence Quantification was done by line method.

As a result, its redox potential as a bleaching agent is 0. 15
When using V or more (1.3-DPTA-Fe
, GEDTA-Fe) was found to have particularly excellent desilvering properties.

Example 10 Samples 021 to 35 prepared in Example 6 were treated with bleaching solutions of pH 4.0, 5.0 and 6.0 in the same manner as in Example 5, and the resulting samples were treated as in Example 5. Similarly (dark and humid heat preservation =
The samples were stored at 60° C., 70% Rll for 10 days), and the increase in stain in the unexposed areas was evaluated in the same manner as in Example 5.

As a result, a photosensitive material satisfying the constitution of the present invention with pn5.0
When processing with the following bleaching solution, there was clearly less increase in staining during image storage after processing.

Claims (2)

[Claims] (1) Each support has at least one red-sensitive silver halide photosensitive layer, one green-sensitive silver halide photosensitive layer, and one blue-sensitive silver halide photosensitive layer, and the photosensitive layer closest to the support and the top of the support The dry film thickness of the non-photosensitive layer provided between the undercoat layer is 2.5 μm or less, and the red-sensitive silver halide photosensitive layer contains a high boiling point organic solvent with a dielectric constant of 6.0 or less. When carrying out color development, desilvering, and fixing processes on silveride color photographic materials after imagewise exposure, the pH of the processing bath for the desilvering process is
5.0 or less, a method for processing a silver halide color photographic material. (2) The acetic acid concentration in the treatment bath for the above desilvering treatment is 1 mol.
According to claim (1), the concentration of the aminopolycarboxylic acid ferric complex salt having a redox potential of 150 mV or more and a redox potential of 150 mV or more at pH 6.0 is 0.1 mol/l or more. A method for processing silver halide color photographic materials.