JPH03150563A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve malodor of a processing solution and an adverse effect on a processing machine and to suppress occurrences of bleach fog and stains during storage after processing by incorporating an oxidant and a specified monobasic carboxylic acid in a processing solution having bleaching ability. CONSTITUTION:The processing solution having bleaching ability contains the oxidant and the monobasic carboxylic acid having at least one nondissociable hydrophilic substituent and a hydrophobic parameter of <= 0. The introduction of the substituent greatly reduces the vapor pressure of the acid in an aqueous solution and prevents photographic performance from being adversely affected even at the time of adding a large amount of the acid, and substantially prevents occurrence of malodor and corrosion of the parts of the processing machine due to this evaporated acid, thus permitting problems caused by evapo ration of the acid, and further, bleach fog and stains after the processing to be improved, and rapid desilvering to be executed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Use) The present invention relates to a method for processing silver halide color photographic materials, and more specifically, the present invention relates to a method for processing silver halide color photographic materials, and more specifically, it relates to a method for processing silver halide color photographic materials, and more specifically, it relates to a method for processing silver halide color photographic materials. The present invention relates to a processing method that can perform rapid desilvering, which has improved effects on the processing equipment and the processing equipment that uses the same, and which has also improved the occurrence of bleaching blade blur and staining during image storage after processing.

(Prior Art) In general, the basic processing steps for silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials R [7]) consist of a color development step and a desilvering step. In the color development step, imagewise exposed silver halide is reduced by an aromatic primary amine color developing agent to yield silver, and the oxidized color developing agent reacts with a color former (coupler) to form a dye image. give. Next, in the desilvering step, the silver produced in the color development step is oxidized with an oxidizing agent, and then dissolved by a silver ion complex forming agent called a fixing agent. Through this desilvering step, only the dye image remains on the color photosensitive material.

In the actual development process, in addition to this basic process, hardening baths, stopping baths, image stabilizing baths, Water washing baths etc. are provided.

The above-mentioned desilvering step can be carried out using a two-bath method consisting of a bleach bath containing an oxidizing agent and a fixing bath containing a fixing agent, a method using a bleach-fixing bath containing an oxidizing agent and a fixing agent, or a combination thereof. There are methods etc. Further, each treatment bath may be composed of a plurality of treatment tanks.

This bleaching solution and bleach-fixing solution contain an oxidizing agent (bleaching agent) for oxidizing silver reduced in the color development process and an acid for adjusting the processing solution to an appropriate pH. Conventionally, acetic acid has been mainly used as this acid from the viewpoint of not reducing desilvering properties and from the viewpoint of photographic properties. However, since the vapor pressure of acetic acid is not very high, it is usually heated at 35°C to 45°C.
Processing solutions with bleaching properties that are used for processing, aeration, etc. are easily vaporized, and the odor is harmful to worker safety and environmental protection, and the evaporated acid can cause damage to processing machine parts, peripheral equipment, and appliances. gold Ii1 corrosion or deterioration,
There were problems such as promotion.

In recent years, small over-the-counter service systems called minilabs have become popular. Such minilabs are often installed in front of stores such as supermarkets, and
The 8 works are not done by workers who have specialized knowledge, but are concerned with odor, worker safety, environmental conservation, and other concerns. Metal corrosion and deterioration of machines and peripheral equipment has become a major problem.

On the other hand, minilabs are strongly required to shorten the processing time in order to quickly respond to customer requests.

In this respect, there is a strong desire to shorten the time required for the desilvering process, which occupies most of the conventional processing, and within this, there is a need to speed up the bleaching process.

However, ethylenediaminetetraacetic acid ferric complex salt (hereinafter referred to as EDTA-Fe(In)-), which is the main oxidizing agent used in bleach and bleach-fix solutions, has a basic drawback of weak oxidizing power. Therefore, despite various improvements such as the combined use of bleaching accelerators, the demand for faster processing has not been fully met. It is well known that in order to shorten the bleaching time, it is sufficient to use an oxidizing agent with strong oxidizing power. Examples of such oxidizing agents include inorganic compounds such as red blood salts, ferrous chlorides, persulfates, and dichromates, and 1,3-diaminopropanetetraacetic acid among ferric aminopolycarboxylic acid complex salts. Ferric complex salt (hereinafter referred to as 1.3-PDTA-Fe (l
It) and glycol ether diamine tetraacetic acid ferric complex salt (hereinafter referred to as GEDTA .F e (Ill)) are known. Among these, from the viewpoint of environmental protection and handling safety, the development of bleaching technology using the above-mentioned strong oxidizing aminopolycarboxylic acid ferric complex salt as an oxidizing agent is underway. Regarding these, please refer to JP-A-62-2
No. 22252 Yarisachi Disclosure (Rese
Arch Disclosure) No. 24023
etc. are listed.

However, when the color development process using an aromatic primary amine color developing crude drug is followed by processing with a processing solution that has bleaching ability and consists of such a strong oxidizing agent, the film is carried into the processing solution that has bleaching ability. There was a major problem in that color developing agents were oxidized and further reacted with color formers, resulting in significant color staining called bleaching.

These can be found in The Theory of Fumetographic Process, The Fourth Edition, and James (The Theory or Photographic Process).
l+1cProcess Fourth 1iditi
on, Jalles), p. 452.

In order to avoid this, a stop bath or a water washing bath may be provided after color development to remove the color developing agent in the film, and then bleaching or bleaching may be performed.

However, this involves an increase in the processing bath and its waste liquid, and the original objective of shortening the processing time cannot be achieved.

Furthermore, apart from this problem of bleaching fog, when processing in a shortened time using a processing solution with such bleaching ability,
A problem arises in that the processed color light-sensitive material exhibits significant staining during storage.

As a means to solve the problem of occurrence of bleach blade blur and stain, a method of lowering the pH of the bleach solution to 1.5 to 5.8 is disclosed in Japanese Patent Application Laid-Open No. 1-213657. Also, NA similar to this is Eastman Kodak's C-
41RA treatment (a bleaching solution containing 1,3-PDTA.Fe(III) and acetic acid and having a pH of approximately 4.3) is also used.

(Problems to be Solved by the Invention) However, these techniques do not sufficiently solve the above problems, and in order to significantly lower the pH of the bleaching solution, a large amount of acid such as acetic acid must be used. However, the aforementioned problems such as deterioration of the working environment and metal corrosion and deterioration of processing machine parts, peripheral equipment, tools, etc. were even bigger problems.

Therefore, the first object of the present invention is to provide a processing solution with bleaching ability that improves problems such as deterioration of the working environment such as odor and metal corrosion due to evaporated acid without deteriorating photographic properties related to bleaching. It is about providing.

7- The second object is to provide a processing method that achieves the first object and can perform rapid desilvering with improved bleaching edge burrs and post-processing stains.

(Means for Solving the Problems) The present inventors have discovered that the above UA problem can be achieved by the following method.

(1) In a method of processing an imagewise exposed silver halide color photographic light-sensitive material with a processing liquid having bleaching ability after color development, the processing liquid having bleaching ability contains no oxidizing agent and no hydrophobicity parameter. A method for processing a silver halide color photographic light-sensitive material, which comprises a monobasic carboxylic acid having at least one non-dissociable hydrophilic substituent as described below.

(2) The method for processing a silver halide color photographic light-sensitive material according to claim (1), wherein the oxidizing agent of the processing solution having bleaching ability is an oxidizing agent having a redox potential of 130 mV or more.

(3) The silver halide color photographic photosensitive material according to claim (1), wherein the oxidizing agent of the processing solution that improves the bleaching ability is an aminopolycarboxylic acid ferric complex salt having a redox potential of 130 mV or more. How materials are processed.

(4) The pH of the processing liquid having bleaching ability is 2.5 or more.5.
5 or less (a method for processing a silver halide color photographic material according to claim 1).

The present invention will be explained in detail below.

A typical desilvering step after color development is as follows.

■ Constant wearing of bleach bath ■ Bleach bath - bleach-fixing bath ■ Constant wearing of bleach bath - washing bath ■ Constant wearing of bleach bath - bleach-fixing bath ■ Bleach-fixing bath Here, each bath may contain two or more types ( For example, 2
~4 tanks). When the treatment bath is composed of two or more types, it is preferable to adopt a countercurrent replenishment system.

Although a water washing bath may be provided between the above-mentioned desilvering step and color development step, it is preferable that the desilvering treatment step be performed immediately after color development in order to greatly achieve the effects of the present invention such as rapidity.

Among the above steps ■～■, steps ■、■、
■ is preferred. Regarding process
-75362. Regarding process ■,
For example, 68 is shown in Japanese Patent Application Laid-open No. 143755/1983. The monobasic carboxylic acid having at least one non-dissociable hydrophilic substituent and having a hydrophobicity parameter of 0 or less according to the present invention can be applied to any treatment liquid having bleaching ability.

The monobasic carboxylic acid (hereinafter referred to as the monocarboxylic acid of the present invention) having at least one non-dissociable hydrophilic substituent and having a hydrophobicity parameter (j!ogP) of O or less according to the present invention will be described below.

The hydrophobicity parameter is a parameter introduced by Ilansh et al. and is described in "Structure-Activity Relationship of Drugs", Chemistry Region, Special Edition No. 122 (1979). In the present invention, the vapor pressure of carboxylic acid in an aqueous solution is significantly reduced by introducing a substituent having a hydrophobic parameter of 0 or less, and even when added to a processing solution having bleaching ability in large quantities, it does not adversely affect photographic properties. This essentially solves the problems of odor generation and evaporated acid corroding parts and peripheral equipment of the processing machine.

At least one non-dissociable hydrophilic substituent having a hydrophobicity parameter (fogP) of O or less includes a hydroxyl group, an optionally substituted alkoxy group, a carbamoyl group, a sulfonyl group, a sulfone group, and a ureido group. . Among these, hydroxyl group, alkoxy group and ureido group are preferred.

The monobasic carboxylic acids having these substituents are aliphatic, aromatic or heterocyclic monocarboxylic acids. Here, aliphatic refers to straight chain, branched or cyclic aliphatic hydrocarbons, and includes saturated and unsaturated hydrocarbons. Examples of aromatics include benzene and naphthalene, which may be substituted. The heterocycle is a cyclic compound containing nitrogen, oxygen, and sulfur, and typical examples include pyridine, furan, and thiophene, which may be substituted. Among these, aliphatic has 1 carbon number
-8 are preferable, and alkylcarboxylic acids having 1 to 4 carbon atoms are more preferable. In the aromatic group, I preferably has 6 to 15 carbon atoms, more preferably 6 carbon atoms.
~8 substituted or unsubstituted benzenecarboxylic acids are preferred. As the heterocycle, substituted or unsubstituted pyridinecarboxylic acid is preferred.

The monocarboxylic acid of the present invention not only does not inhibit bleaching compared to other polyvalent carboxylic acids (excluding aminopolycarboxylic acids), but also has improved desilvering properties in a series of subsequent desilvering steps, It has excellent performance in achieving speed.

Specific examples of the monocarboxylic acid of the present invention are shown below, but the present invention is not limited thereto.

(1) (2) (3) (4) (5) (6) HOCH, COOH CH, OCH, COOH CH.

HOCHCOOH CHICON HCHzCOOH HtN CON HCH,COOH HffiNCO(cHz)zcooH 12 (7) (8) (9) (10) (11) (12) (13) H2N CO(CHt ) COOH CzHsOCH zCOOH HOCH□CH, COOH CH3C (CH3 ) (OH) C00H1-1,
N CON HCH2C111C00HCHy CO(
CHt ) x COOHC(CH3)xc (OH)
COOH Among these, hydroxyacetic acid and lactic acid are particularly preferred.

The monocarboxylic acids of the present invention may be used alone or in combination of two or more. In addition, known acids other than those mentioned above (for example, acetic acid,
Propionic acid, citric acid, malonic acid, oxalic acid, hydrochloric acid,
(isoacetic acid, alanine, sulfuric acid, nitric acid, phosphoric acid) can be mixed and used as long as the amount thereof is less than the molar amount of the monocarboxylic acid of the present invention. As the acid used in combination, acetic acid and propionic acid are preferred.

The amount of the monocarboxylic acid used in the present invention is the amount necessary to quickly bring the pH of the processing solution with bleaching ability to the level where it exhibits its original performance, and preferably, The amount is 0.2 mol or more and 3.0 mol or less, more preferably 0.4 mol or more and 2.5 mol or less per 112 mol. Particularly preferably, it is 0.6 mol or more and 2.0 mol or less. Preferably, the monocarboxylic acids of the invention are used in bleaching solutions. In the case of a bleaching solution, the amount is particularly preferably 0.6 mol or more.

Preferred examples of the combined use of the monocarboxylic acid of the present invention and other acids include the combined use of hydroxyacetic acid or lactic acid and acetic acid or propionic acid. As mentioned above, when acetic acid and propionic acid are used in high concentrations, they cause significant odor and metal corrosion, but if the concentration is kept below 0.7 mol/l and the monocarboxylic acid of the present invention is used in combination, these problems will not occur. , and improved processing performance for bleaching blade burrs and post-processing stains, which is the object of the present invention, can be obtained. In this case, the molar ratio of acetic acid or propionic acid to the monocarboxylic acid of the present invention used is 0.1-1.0, preferably 0.2-1.0.
It is 0.7.

The redox potential of the oxidizing agent described in the present invention is a value measured at pH 6.0. This measurement is based on the Transactions of the Faraday Society.
sacLions of the FaradaySo
55 (1959), 1312-1
313rL and is expressed in terms of the standard hydrogen electrode potential. In the case of chelating compounds such as aminopolycarboxylic acid ferric complexes, extreme pH
Depending on the conditions, chelate compounds may undergo deterioration due to hydrolysis, protonation, etc., so care must be taken when measuring the redox potential. For more information on these changes in EDTA Fe(T[l), see The Theory of Photographic Processes.

Humes Edition, James (The The
ory5 of Photographic Process F
ours udiLionJa+nes), 295~
296 true. For this reason, in the present invention, an oxidation-reduction potential at pH 6.0 was used.

The monocarboxylic acid of the present invention used in the treatment liquid having bleaching ability of the present invention can be used together with a known oxidizing agent. Specifically, EDTA/Fe(Ill) (redox potential 110 mV), diethylene I/lyaminepentaacetic acid ferric complex salt (redox potential 80 mV), trans-1,
2-Cyclohexanediaminetetraacetic acid ferric complex salt (oxidation-reduction potential 80 mV, hereinafter referred to as Cy IIDTA ・F e (
Oxidizing agents with a redox potential of 130 mV or more, such as red blood salts, ferric chloride, dichromates, persulfates, bromates, etc., and aminopolycarboxylic acids. Some organic compounds of ferric complex salts can be mentioned. In the present invention, an oxidizing agent having an oxidation-reduction potential of 130 mV or more is preferred from the viewpoint of rapid bleaching.

Furthermore, it is preferable to use a 6-aminopolycarboxylic acid ferric complex salt having an oxidation-reduction potential of 130 mV or more from the viewpoint of environmental protection, handling safety, metal corrosivity, and the like.

As a specific example of an aminopolycarboxylic acid ferric complex salt compound having a redox potential of 130 mV or more, the redox potential (vsNHE, all=6
．． mV) Bis(N-(2-acetamido)iminodiacetic acid) ferric complex salt (abbreviation, 2-^IBA4e (I[l) ) bis(methyliminodiacetic acid) ferric complex salt (abbreviation, former BA4e (III)) Bis (Iminoniacetic acid) ferric complex salt 210 (abbreviation, II
IA-Fe(I[+))1,4-diaminobutane-N,N.

N',N'-acid ferric acetate complex salt (abbreviation, 1.4-DBT^・Pe(III)) diethylenethioetherdiamine-N,N,N",N"-acid ferric acetate complex salt 30 30 80 00 (abbreviation, D[1TEDTA-Fe (m))6,
Glycol ether diamine-N.

N,N',N'-acid ferric acetate complex salt 240 (
Abbreviation: GI! rJTA-Fe (m))7.1.3
-Diaminopropane-N, NN', N'-acid ferric acetate complex salt 250 (abbreviation, 1.3-PDTA
Fe (IT[))8, tris-(2-carboxypyridino)ferric complex salt 3209,
Bis-(2,6-dicarboxypyridino)ferric complex salt
310 and the like. These aminopolycarboxylic acid ferric complex salts can be used alone or in combination of two or more. The oxidizing agent of the present invention preferably has a redox potential of 150 mV or more, more preferably 180 mV or more.

Among these compounds, Nα7 1.
3-diaminopropane-N,N,N',N'-acid ferric acetate complex salt (1,3-PDTA-Fe(■)).

These aminopolycarboxylic acid ferric complex salts are used in the form of alkali metal salts such as sodium and potassium salts, ammonium salts, etc., but ammonium salts are preferred because they bleach the fastest.

The amount of the oxidizing agent used in the treatment liquid having bleaching ability of the present invention is 0.05 mol or more per treatment liquid IA having bleaching ability,
More preferably 0.10 mol or more.

More preferably, the amount is 0.30 mol or more in terms of speeding up processing and reducing bleaching blade blur and stain. However, since the use of an excessively high concentration solution may cause problems such as precipitation, it is preferable to use it in an amount of 1.0 mol or less, and more preferably 0.7 mol or less in view of not inhibiting the bleaching reaction.

Next, the pH of the treatment liquid having bleaching ability of the present invention will be described.

A pllG bleaching solution containing 1,3-IDT8-Fe(III) is described in the aforementioned Japanese Patent Application Laid-Open No. 62-222252. Conventionally, the optimum pH of a bleaching solution containing a ferric aminopolycarboxylic acid complex salt is around p 116 N from both the viewpoint of ensuring a high bleaching rate and preventing poor recoloring of the q cyan dye, and this has been widely practiced. That is, although lowering the pH improves the bleaching rate, it causes poor recovery of cyan dye, so the optimum balance was determined to be around 2116.

On the other hand, the bleaching solution used in the present invention is preferably ρ1155 or less because the effect is effectively exhibited. That is, it solves the conventional problem of being able to achieve rapid desilvering and complete restoration of the cyan dye, which were considered to be contradictory. The pH of the bleaching solution of the present invention is preferably 2.5 to 5.5, more preferably 2.6 to 4.5, most preferably 2.8 to 4.0.
It is. The pH of the bleach-fix solution of the present invention is preferably 5.5 to 8.5, more preferably 6.0 to 8.0.

To adjust the pH to this range, the acids mentioned above are used.

When using a ferric aminopolycarboxylic acid complex salt in a treatment solution with bleaching ability, the aminopolycarboxylic acid may be added in an amount necessary to form a complex with ferric ions, or slightly in excess. It may be added to 0. When added in excess, it is usually preferable to add it in excess within the range of 0.01 to 10 mol%.

In addition, in the treatment solution having bleaching ability of the present invention, when a ferric aminopolycarboxylic acid complex salt having a redox potential of 130 mV or more is used, a ferric aminopolycarboxylic acid complex salt having a redox potential of less than 130 mV is used in combination. You can. Specifically, ferric complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid can be mentioned.

Various bleaching accelerators can be added to the processing liquid having bleaching ability of the present invention.

Such bleach accelerators are described, for example, in U.S. Pat.
No. 2, British Patent No. 1.138,842, Japanese Patent Application Publication No. 1983-
No. 95630, Research Disclosure No. 171
Compounds having a mercapto group or disulfide group described in No. 29 (July 1978 issue), JP-A-50-140
Thiazolidine derivatives described in U.S. Patent No. 129, U.S. Pat.
Thiourea derivatives described in No. 706.561, JP-A-58
- Iodide described in No. 16235, German special kitsuki 2,74
Polyethylene oxides described in Japanese Patent Publication No. 8,430, polyamine compounds described in Japanese Patent Publication No. 8836/1983, and the like can be used. Particularly preferably British Patent No. 1.13
Mercapto compounds such as those described in US Pat. No. 8,842 are preferred.

In addition to bleaching agents and the above-mentioned compounds, the processing liquid having bleaching ability constituting the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium chloride, sodium chloride, ammonium chloride. can include rehalogenating agents such as.

The concentration of the rehalogenating agent is 0.1 to 5 mol, preferably 0.5 to 3 mol, per bleaching solution IP.

Moreover, it is preferable to use ammonium nitrate as a metal corrosion inhibitor.

The replenishment amount of the bleaching solution of the present invention is 200 ml per ml of photosensitive abrasive material.
mj! Hereinafter, preferably 160mff1~]OmP.

The amount of replenishment of the bleach-fix solution of the present invention is per 1rd photosensitive material.
200mn~3000ml, preferably 250ml~1
It is 300m/2.

Further, the bleaching treatment time is 120 seconds or less, preferably 60 seconds or less, and more preferably 50 seconds or less as the time in the solution.

In addition, during the treatment, it is preferable that the treatment liquid having bleaching ability using the ferric aminopolycarboxylic acid complex salt be subjected to air foaming (aeration) to oxidize the produced ferric aminopolycarboxylic acid complex salt.

Aeration of bleaching solutions is already known and is described in Eastman Kodak's Losing pr.
ocess C-41 (1982, Z-121Th1
rd Edition) Page No. BL-2 or Monitoringthe per-forma
nce of the process C-41
Bleach (1982, Z-121D) states that keeping the bleach solution in a completely oxidized state through sufficient aeration is extremely important for preventing desilvering failure and preventing the formation of leucocyan dyes. Described in detail.

That is, the bleaching solution of the ferric aminopolycarboxylic acid complex salt oxidizes the developed silver during running and also receives the color developing solution from the previous step.

To completely oxidize ferrous t-7i salt to ferric t-7i salt through sufficient aeration, it is appropriate to completely oxidize the ferrous t-7i salt. It is believed that.

The oxidation state of aminopolycarboxylic acid iron complex salts such as
The fact that the redox potential is expressed based on a 1 ratio of ferrous ions to ferric ions can be considered based on general knowledge of electrochemistry, and in fact, US Pat. No. 3,773,510 describes EDTA-F e ) has been disclosed that increasing the redox potential in the bleach-fix solution prevents the formation of leucocyan dyes.

The photosensitive material after bleaching is then subjected to a fixing process using a process that has a fixing ability. The fixing process may be a fixer, a bleach-fixer, or a combination thereof.

Fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates such as thorium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, diocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate. Acid salts, thioureas, thioethers, etc. can be used. Among them, it is preferable to use ammonium thiosulfate.

The amount of fixing agent is from 0.3 to 3 mol, preferably from 0.5 to 2 mol, per 11 of the fixing solution.

In addition, from the viewpoint of promoting fixation, the above-mentioned ammonium thiocyanate (rhodan ammonium), thiourea, 1,000 onythyl (
For example, it is also preferable to use 3,6-cythia 1.8 octanediol) in combination, and the amount of these compounds used in combination is from o.oi mol to 0.1 mole per 11 of the fixer or bleach-fixer.
Generally, it is on the order of moles, but in some cases, the fixing promotion effect can be greatly increased by using 1 to 3 moles.In fixers or bleach-fixers, it can be used as a preservative! lli sulfates, such as sulfite, potassium sulfite, ammonium sulfite, and bisulfite acetate adducts of hydroxylamine, hydrazine, aldehyde compounds, such as acetaldehyde sulfite. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as preservatives, JP-A-61-]/13.0/ It is also preferable to use the sulfinic acid compounds described in No. 18.

The bleach-fixing solution used after the bleaching solution may contain the above-mentioned known bleaching agents. Preferably redox potential 13
It is an aminopolycarboxylic acid ferric complex salt with a voltage of less than 0 mV.

In the bleach-fix solution carried out after the bleach solution, the amount of bleach per bleach-fix solution IP is 0.01 mol to 0.5 mol, preferably 0.02 mol to 0.3 mol, particularly preferably It is 0.03 to 0.2 mole.

In the present invention, the bleach-fix solution (mother liquor) may be prepared by mixing an appropriate amount of separately prepared bleach solution and fix solution at the start of processing, or by dissolving the compound used in the bleach-fix solution in water. It may also be prepared by

The pf of the fixer is preferably 5 to 9, more preferably 6.
5 to 8 are preferred. Further, the pH of the bleach-fixing solution used after the bleaching solution is preferably 5.5 to 8.5, more preferably 6.0 to 8.0.

The amount of replenishment of the bleach-fix solution after fixing solution and bleaching solution depends on the amount of light-sensitive material in? 300ml to 3000 per
ml! is preferable, more preferably 300rr+4!
It is 1300mj2.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixer and bleach-fixer for the purpose of stabilizing the solution.

The shorter the total processing 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, the time is 1 minute 30 seconds to 3 minutes 27 seconds. The treatment temperature is 25°C to 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is increased and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that stirring is possible or strengthened 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, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of processing liquid with the emulsion surface of a photosensitive material, as described in JP-A No. 62-183461.
183461 A method of increasing the stirring effect using a rotating means, and further 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. method, and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective in all bleaching solutions, bleach-fixing solutions, and fixing. It is believed that stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate.

8. The agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the bleach accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258, No. 60-1912
It is preferable to have the photosensitive material conveying means described in No. 59. As described in JP-A-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 in 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 effect of the present invention is remarkable when the total development processing time is short, and specifically, it is clearly exhibited when the total development processing time is 8 minutes or less, and when it is 7 minutes or less, it is even more effective than the conventional processing method. The difference becomes noticeable. Therefore, in the present invention, the total treatment time is preferably 8 minutes or less, particularly 7 minutes or less.

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

A preferred example is a p-phenylenediamine derivative,
Representative examples are shown below, but the invention is not limited thereto.

D-I N N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N[β-hydroxyethyl]amino]aniline D-64-amino-3-methyl-N-ethyl-N- [β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N N-dimethyl-P-phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-ethoxyethylaniline D-114-amino-3-methyl-N-ethyl N-β-
Butoxyethylaniline Among the above ρ-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Also, Gorera's p-phenylenediamine t? , 'J may be a salt such as sulfate, hydrochloride, sulfite, P-1-luenesulfonate. The amount of the aromatic primary amine color developing agent used is preferably in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per 11 color developing solutions.

In addition, the color developer contains sodium sulfite and preservatives.
Sulfites such as potassium sulfite, sodium bisulfite, potassium bisulfite, potassium metasulfite, and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary.

The preferable amount of preservative added is 0.5 per 11 parts of color developer.
g to Log, more preferably 1 g to 5 g.

In addition, as compounds that directly preserve the aromatic primary amine color developing agent, various hydroxylamines, hydroxamic acids described in JP-A-63-43138, and JP-A-63-43138 can be used.
Hydrazines and hydrazides described in -146041 and 63-170642, phenols described in 63-44657 and 63-58443, and G3-4
α-hydroxygetones and α-aminoketones described in No. 4656, and/or various tl! described in No. 6136244. It is preferable to add In addition, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254
No. 63-21647, No. 63-146040,
2 monoamines described in No. 63-27841 and No. 63-25654, No. 63-30845, No. 63-146040,
Diamines described in No. 61-43139, etc., No. 63-
Polyamines described in No. 21647 and No. 63-26655, polyamines described in No. 63-44655, No. 6
Nitroxy radicals described in No. 3-53551, No. 63
It is preferable to use the alcohols described in G-43140 and G156654, and the tertiary amines described in G156654, and the tertiary amines described in G156654.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in No. 349, United States Special Kitsuki 3,
The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developing solution used in the present invention preferably has a pH of 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 pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate J1, boric acid salt, Potassium borate, sodium tetraborate (porax), potassium tetraborate,
Sodium O-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), etc. can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol/1 or more, particularly 0.1 mol/! ~0.4
Particular preference is given to mol/l.

In addition, various clearing agents can be used in the color developing solution as calcium and magnesium precipitation inhibitors or to improve the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, dielenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1 .2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2-
Phosbobutane-1,2,4-)licarboxylic acid, 1-hydroxyedylidene-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, it is about 0.1 g to 10 g per 1j2.

Any development accelerator can be added to the color developing solution if necessary. However, the color developing solution of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, preparation properties, and prevention of color staining. here"
"Substantially" means containing less than 2 ml per developer solution, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 31-16088, No. 37-5987, No. 3 (1-7826, No. 41).
No. 12380, No. 45-9019 and U.S. Patent Box 3,
813,247, P-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50137726, JP-A-44-30074, JP-A-44-30074; Quaternary ammonium salts represented in No. 56-156826 and No. 52-43429, etc., U.S. Patent Box 2.4
No. 94,903, No. 3.128182, No. 4,230
, No. 796, No. 3.253.919, Special Publication No. 1977-1
No. 1431, U.S. Patent Box 2. ．． No. 182.546, same 2
, 596,926 and 3.582.346, etc., Japanese Patent Publication No. 37-16088, 4
No. 2-25201, U.S. Patent Box 3,128,183;
Polyalkylene oxides shown in Japanese Patent Publication Nos. 41-11431, 42-23883, U.S. Pat. Can be done.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic anti-capri agents include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightener, 4°4'-diamino-2,2'-disulfostilbene compounds are preferred.

The amount added is O~5g/1. Preferably 0.1g to 4g/l
It is.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developing solution 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 and 15 seconds.

It is preferable that the amount of replenishment is small, but 10 per IM of photosensitive material
0-1500mf preferably 100-1O00mj! It is. More preferably 200mj! ~900mA.

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. The black-and-white developer used at this time is a so-called black-and-white first developer used in the commonly known reversal processing of color photosensitive materials. Various well-known additives that are used in black-and-white developing solutions used in processing solutions for black-and-white silver halide light-sensitive materials can be included in the black-and-white first developer for color reversal light-sensitive materials.

Typical additives include developing agents such as 1-phenyl-39 pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and alkalis such as sodium hydroxide, sulfur and lithium carbonate, and potassium carbonate. A developer consisting of an accelerator, an inorganic or organic inhibitor such as potassium bromide, 2-methylbenzimidazole or methylbenzthiazole, a water softener such as a polyphosphate, trace amounts of iodide or a mercapto compound. I can give you medication.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. The rinsing water used in the rinsing step, which can be carried out using a simple treatment method, can contain known additives as necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
n side, anti-bacterial 7 that prevents the growth of various bacteria and algae
PJ (e.g. intiazolone, residual chlorine disinfectant,
benzotriazole, etc.), a surfactant to prevent drying load and unevenness, etc. Or L
,E.

14esL, “Water QualiLy Cr
1teria”, Phot, Sci.

and [! ng,, vol1. 9. Na6. pa
Compounds described in GE 344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, Polmarine), etc. can be used. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and Al, optical brighteners, chelating agents (for example, l-hydroxyethylidene-1,1-diphosphonic acid), bactericides, anti-fouling agents, etc. as necessary. Hardeners, surfactants, alkanolamines, etc. can be used.

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 amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

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 have an Mg concentration of 5/1 or less, water that has been sterilized with halogen, an ultraviolet sterilizing lamp, or the like.

In each of the above processing steps for color photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to browning may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes noticeable. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

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.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number and order of emulsion N and non-light-sensitive layers.A typical example is to place multiple silver halides with substantially the same color sensitivity but different sensitivity on the support. A silver halide photographic light-sensitive material having a light-sensitive layer consisting of an emulsion layer, the light-sensitive layer being a unit light-sensitive layer sensitive to blue light, green light, or red light, and having a multilayer halogen In silver compound color photographic light-sensitive materials, the unit photosensitive layers are generally arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive 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. 59-113440, No. 61-20037, No. 6! -20038 Akira m'3
Coupler as described in Drl? Compounds, etc. may be included, and color mixing inhibitors, ultraviolet absorbers, stain inhibitors, etc., which are commonly used, may be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
Western German special Kitsuki 1.121.470 or British special Kitsuki 9
As described in No. 23,045, a 2N configuration of a high-speed emulsion layer and a low-speed emulsion layer can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A No. 571
No. 12751, No. 62-200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity 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 (B H) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL ) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL),
Alternatively, they can be installed in the order of BH/BL/GL/GH/RH/RL, or in the order of BH/BL/(1;H/GL/RL/RH).

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of RH/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

Furthermore, 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 a silver halide emulsion layer with higher sensitivity 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, with the photosensitivity gradually decreasing toward the support. Even when composed of 3N having different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion N/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

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

Any of these layer arrangements can be used in the color photosensitive material of the present invention, but in the present invention, the dry film thickness of all constituent layers of the color photosensitive material excluding the support and the undercoat layer and back layer of the support is 20.0 μm. The following is preferable in order to achieve the object of the present invention. More preferably 18.0
It is less than μ.

These film thickness regulations are determined by the color developing agent that is incorporated into these layers of the color photosensitive material during and after processing. By making a big impact. In particular, the increase in magenta color, which is thought to be caused by the green-sensitive color layer, is greater than the increase in color of other cyan and yellow colors.

Note that it is desirable that the lower limit value in the film thickness regulation be reduced within a range that does not significantly impair the performance of the photosensitive material based on the above regulation. The lower limit of the total dry film thickness of the constituent layers of the photosensitive material excluding the support and the undercoat layer of the support is 12.0μ, and the lower limit of the total dry film thickness of the constituent layers excluding the support and the undercoat layer of the support is 12.0 μm. The lower limit of the total dry film thickness of the constituent layers is 1.0μ.

Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer.

The film thickness of the multilayer color photosensitive material in the present invention is measured by the following method.

The photosensitive material to be measured is kept under conditions of 25°C and 150% RH 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 as the total thickness of the coated material excluding the above-mentioned support. The thickness of the layer. This thickness can be measured using, for example, a film thickness measuring device (Anrit) using a contact-type piezoelectric transducer.
us Electric Co.

Ltd., K-402B 5tand, ). Furthermore, on the support! lI! Removal of the 11 layer can be performed using an aqueous sodium hypochlorite solution.

Next, use a scanning electron microscope to take a cross-sectional photograph of the sensitive material (magnification is preferably 3,000 times or more), measure the total thickness on the support and the thickness of each layer, and calculate the previous film thickness. The thickness of each layer can be calculated by comparing it with the total thickness measured by the measuring device (absolute value of the actual thickness).

Swelling rate of the sensitive material of the present invention [(equilibrium swelling film thickness at 25°C1II20 - dry total film thickness at 25'C, 55% RH/dry total film thickness at 25'C, 55% RH) xloo )
is preferably 50 to 200%, more preferably 70 to 150%. If the swelling ratio deviates from the above value, the amount of color developing agent remaining will increase, and this will have an adverse effect on photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Furthermore, the swelling speed of the photosensitive material of the present invention is 90% of the maximum swelling film thickness in the color developing solution (30°C, 13 minutes and 15 seconds).
When 0% is the saturated swollen film thickness and the time required to reach 1/82 of this is defined as the swelling rate T%, T'A is preferably 15 seconds or less. More preferably, T'A is 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention may have any silver halide composition. That is, silver chloride, silver chlorobromide, silver iodobromide, silver iodochloride, or silver iodochlorobromide.

Preferred silver halides are silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing up to about 30 mole percent silver iodide.

Particularly preferred is silver iodobromide 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. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, 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. 176.
43 (December 1978), pp. 22-23, "T. Emulsion preparation.
and types)” and same No. 18716 (
(November 1979), 64B pages, ``Physics and Chemistry of Photography'' by Graff, 1-de, published by Beaumontel (P, Gl.
afkidesChemic at Ph1siqua
PhotoHraphjque r'aul Mon
te11967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin, I
'hoLo5raphicEmulsion C1+e
mistry (Focal Press + 196
6)), Zelikman et al. [Production and coating of photographic emulsions], published by Focal Press (V, L, Zelikman
et al.

MakinI! and Coating Photo
rapicl! mulsion Focal Pre
ss + 1964).

U.S. Special Kitsuki No. 3,574.628, No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Tokukitsuki No. 1.413 748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering (Gutoff, Photographic Sc.
14, pp. 248-257 (1970); U.S. Pat.
, 433.048, 4,439,520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a phase structure, or silver halides of different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The additives used in this process are described in Research Disclosure No. 17643 and No. 18716, and 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.

2 RD17643 Page 23 Chemical sensitizers Sensitivity enhancers Spectral sensitizers, supersensitizers Brighteners Antifoggants and stabilizers Light absorbers, 7 pages 25-26 Ilter dyes UV absorbers Anti-stain agents Dye image stabilization Hardener Binder Plasticizer, Lubricating coating aid, Surface active agent Anti-sulfuric agent Page 27 Page 24 Page 24-25 Page 23-24 Page 25 Page right column Page 25 Page 26 Page 26 Page 27 Page 26-27 D8716 648 Page right column Same as above Page 648 Right column - Page 649 Right column Page 649 Right column - Page 649 Right column - Page 650 Left column Page 650 Left - Right column Page 651 Left column Same as above Page 650 Right column Same as above Same as above The present invention includes various aspects. A color coupler can be used, and a specific example thereof is the above-mentioned RDN [L17643, ■-C-
It is described in the patent described in G.

Yellow couplers include, for example, U.S. Patent Section 3.93.
No. 3,501, No. 4,022,620, No. 4,326
, No. 0211, No. 4,401.752, No. 4,24
8,961, Japanese Patent Publication No. 58-10739, British Patent No. 1.425,020, British Patent No. 1.476.760 (U.S. Patent Section 3.973968, British Patent No. 4,314,023,
4,511.649, European Patent No. 2. '19,47
Those described in No. 3A etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and European Patent No. 73,6
No. 36, U.S. Patent Section 4,310°619, No. 4,35
No. 1,897, No. 3,061.432, No. 3.725
, No. 064, No. 4500.630, No. 4,540,6
No. 54, No. 4.556,630, RD HCL24
220 (June 1984), RD No. 2423
0 (June 1984), Japanese Patent Publication No. 60-33552,
No. 6043659, No. 61-72238, No. 603
5730, No. 5-118034, No. 60-185
Particularly preferred are those described in No. 951, WO (PCT) No. 88104795, and the like. The effects of the present invention on bleaching and staining are particularly remarkable for viraduroazole couplers.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat.
No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929,
2,801,171, 2,772,162, 2,895,826, 3,772,002, 3
, 758°308, 4,334,011, 4,
No. 327.173, West German Patent Publication No. 3,329,729
European Patent Section 121.365A, European Patent Section 249°453
No. A, U.S. Patent Section 3.446.622, 4,333.
．． No. 999, No. 4,753,871, No. 4,451,
No. 559, No. 4,427.75 No. 67, No. 4.690,889, No. 4,254゜21
No. 2, No. 4,296,199, JP-A-61=4265
Those described in No. 8 etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes include RD No., ■-G term of +7643, U.S. Pat. 4,138.258
Preferred are those described in British Patent No. 1.146368. Also, couplers that compensate for the non-absorption of coloring dyes by means of fluorescent dyes released during coupling as described in U.S. Patent Section 4.774,181, and
It is also preferable to use a coupler described in No. 7120 which has a dye precursor group capable of reacting with a developing agent to form a dye as a breakaway group.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． Preference is given to those described in European Patent No. 570, European Patent No. 96.570 and German Patent Publication No. 3.234,533.

6- Typical examples of polymerized dye-forming couplers include U.S. Pat.
It is described in 4,367.282, 4,409.320, 4,576.910, British Patent 2,102,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, No. 63-37346, U.S. Patent No. 4,248,962
No. 4782.012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140, British Patent No. 2,131,188, JP-A-59-157638,
The one described in No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4□130.427, U.S. Pat.
4.338,393, 4.310,618, etc. DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc.; DIR coupler-emitting coupler, D
IR coupler releasing redox compound or Dlr?
Redox-releasing redox compounds, European Patent Section 173.
RDNα114/19, RDNα114/19, RDNα114/19, RDNα114/19, RDNα24241, JP-A-6
1-2012/17η, etc., Gantt-releasing couplers described in U.S. Pat. Patent Section 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 light-sensitive material by various known dispersion methods.

Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322.027, etc.; Specific examples of boiling point organic solvents include phthalate esters (dibutyl phthalate-1, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(24-di-L-amyl phenyl) phthalate, bis(2 , 4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, etc.) Tricyclohexyl bosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl bosphate, di-
2-ethylhexyl phenylbospone-1-, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzyl-1, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecanamide, N, N-diethyl laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.4
-diterL-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyl 1-, isostearyl lafti 1-, trioctyl citrate, etc.), Ayu 9 F11 bodies (N N-diptyl-2-butoxy-5LerL octylaniline, etc.),
Examples include hydrocarbons (paraffin, dodecylbenzene, diisopropylnafculene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Organic solvents with a temperature of C or more and about 160'C or less can be used.
Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclobeny1-zanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation are disclosed in U.S. Pat.
41,230, etc.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO38100723 are used. In particular, the use of acrylamide-based polymers is preferable for stabilizing color images, etc. The present invention can be applied to various color photosensitive materials. It is particularly preferable to apply the present invention to color negative films for general use or movies, and color reversal films for slides or televisions.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D.

No. 17643, page 28, and No. 1871
6, from the right column on page 647 to the left column on page 648.

(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 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/n (unit of silver) for silver halide, colloidal silver, and coupler, and the amount expressed in g/n (unit) of silver for silver halide, colloidal silver, and coupler, and the amount expressed in moles per 1 mole of silver halide in the same layer for sensitizing dye. Shown in numbers.

1st layer; antihalation layer black colloidal silver Silver coating amount 0. 2 Geradine 2.2UV-10,I Ul-20,2 Cpd-10,05 Solv-10,01 Solv-20゜5olv-30゜Second layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07/ /) Silver coating amount 0
゜1 8 5 Gelatin 1.0Cpd-2
0.2 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion (48110.0 mol%, internal height GL type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, I4 hedral grains ) Silver coating amount 0.26 silver iodobromide emulsion (Af! 14.0 mol%, internal high AgI type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, 14-hedral grains) Silver coating amount 0 ．． 2 gelatin
1.0ExS-14,5XI
O-'f4 ExS -21,5 -30,023 ExC-60,14 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag 116 mol%, internal high Agl type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, Plate-shaped particles, diameter/W ratio 4.0) Silver coating amount 0.55 Gelatin 0.7ExS-13
X10-'ExS-21XIO-'ExS-30,3X10-'ExS-40,3X10-' ExC-30,05 ExC-40,10 ExC-60,08 5 5th layer: 3rd red-sensitive emulsion layer Odor Silver oxide emulsion (Agl O, 0 mol%, internal high Ag
L-type, equivalent sphere diameter 1.2 μ, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter/thickness ratio 6.0) Silver coating amount 0.9 0.6 2X10-' 0, 6X10-' 0, 2X10-' 0,07 0,06 0,12 0,12 Gelatin xS-I xS-2 xS-3 ExC-4 ExC-5 Solv-I 0Iv-2 6th layer: Intermediate layer gelatin pd-4 7th layer : First green-sensitive emulsion layer silver iodobromide emulsion (Agl 10.0 mol%, internal height A
GL type, ball equivalent diameter 0. 7 μ, 6 1.0 0° Coefficient of variation of 0° sphere equivalent diameter 14%, I4 hedral grain) Silver coating amount 0.2 silver iodobromide emulsion (Agl 14.0 mol%, internal height GL type, sphere equivalent diameter 0 .4μ, coefficient of variation of equivalent sphere diameter 22%, I4-hedral particles) Silver coating amount 0. 1 gelatin
1. 2ExS-55xto
-'ExS-62xlO-'ExS-71XIO-' ExM-10,20 ExM-60,25 ExM-20,10 ExM-50,03 Solv-10,40 Solv-50,03 8th layer: 2nd green feeling Emulsion layer Silver iodobromide emulsion (Ag 110 mol%, internal high iodine type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) Silver coating amount 0 .4 Gelatin 0.35ExS-5
3,5×10-'ExS-61,4×10-'ExS-70,7XIO-' ExM-10,09 ExM-30, (N Solv-10,15 Solv-50,03 9th layer: Intermediate layer Gelatin 0/5 1st θ layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (Agl l O, 0 mol %, inner high gl type, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%, Plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.0 Gelatin 0.8EχS-
52X10-' ExS-60°Ext-70°ExM-3 ExM-4 xC-4 Solv-1 11th layer; Yellow filter layer p d-3 Gelatin Solv-1 12th layer: Intermediate layer gelatin p d-2 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (grlO mol%, internal high iodine type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) Silver coating amount I Silver bromide emulsion (Agl 4.0 mol%, internal high iodine type, equivalent sphere diameter 0.4 sxio-'8X10-' 0, 01 0, 04 0.005 0.2 0, 05 0゜0゜0゜Oo 0゜■ μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.05 gelatin
1. 0ExS-83xlO
-' ExY-10,25 ExY-30,32 ExY-20,02 Solv-10,20 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 19.0 mol%, internal height A
GL type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 16%, tetradecahedral particles) Silver coating amount 0.19 gelatin
0.3ExS-82X10-
' ExY-10,22 Solv-10,07 15th layer: Intermediate layer fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0.13.) 7 〇- Silver coating amount 0.2 Gelatin 0 .36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 14.0 mol%, internal height A
GL type, equivalent sphere diameter 1.5μ, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5.0) Silver coating amount 1.0 Gelatin 0.5ExS-81
,5X10-' ExY-10,2 Solv-10,07 17th layer: 1st protective layer Gelatin V U Solv Solv-2 18th layer: 2nd protective layer Fine grain silver bromide (equivalent sphere diameter 0°07μ) Silver coating amount Gelatin polymethyl methacrylate particles (diameter 1.5μ) -1 -1 pd-5 V CH3Cl13 +CH, -C-) -10 CH2-C→-0 0OCH3 V xM t xC l1 3 xC xC 0■ xC i1 4 xC 7 xC xC 0 ■ IJ2S 5 xM H3 xM 6 xM-4 xM 7 xM xY 8 xY 2 xS 9 xS xS xS ans I ZH5 0 xS xS-8 2H5 1 xS olv ■ olv olv 2 olv 5 pd- 1 pd-2 H pd-3 pd-5 CIIF + , SO□NHCl12CH2CH20C
II□CII□N (Cllz)sCH:+=CH3O
□CH,C0NH C11□ The prepared sample was cut and processed into 35mm width, and the mouth (light source)
Wedge exposure was applied at a color temperature of 4800°K), and processing was performed using a cine-type automatic processor in the processing steps shown below.

However, the samples to be evaluated for performance were subjected to imagewise exposure until the cumulative replenishment amount of the color developer reached three times the volume of the mother solution tank, and then the samples were processed.

At this time, the composition and pH of the bleaching solution were changed as shown in Table 1, and the conditions for the aeration of the bleaching solution were adjusted every time from a piping section with many pores of 0.211IIIφ provided at the bottom of the bleaching solution tank. 200 minutes - The treatment was carried out while foaming.

Processing process Processing time Processing temperature Replenishment amount 1 3 minutes 15 seconds 37.8°C23rt 50 seconds 38.0°C5d 1 minute 40 seconds 38.0”C30d 30 seconds 38.0°C 20 seconds 38.0°C30d 20 seconds 38.0°C2〇- 5- tank capacity 02 5! 0f 5I! .

2 1 Step Color Development Bleach Fixing Washing with water (11 Washing with water (2) Stable drying 1 minute 55 °C 9 Replenishment amount is the amount per 35 mm width 1 m Washing with water is by countercurrent method from (2) to (1) The amount of developing solution brought into the bleaching step and the amount of fixing solution brought into the washing step were 2.5 d and 2.0 ml per 1 meter length of a 35 mm wide photosensitive material, respectively.

Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (B) Replenisher (2)
) Diethylenetriaminepentaacetic acid 1.0 1.0 Hydroxyethylideso 1. I-Diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4 Potassium iodide 1.5d 6-Hydroxylamine sulfate 4-(N-ethyl -N β-hydroxyethylamino) to 2-methylaniline sulfate solution to pH 2,4 4,5 1,0f 10.05 1.01 10.10 (bleaching solution) 1.3-diaminopropanetetraacetic acid Diiron ammonium hydrate 1.3-diaminopropanetetraacetic acid ammonium bromide ammonium nitrate Add water to pH Mother liquor (6) 144.0 2.8 84.0 90.0 1.0ffi Replenisher (6) 206. 0 4.0 120.0 125.0 See Table 1 1.01 See Table 1 (Fixer) Common to mother liquor and replenisher (6) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700g/l 340. Add 0ml water and add 1.01p) (7.0 (Washing water) Mother liquor, replenisher common tap water to H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strong base anion exchange resin (Amberly zRA-40
Water was passed through a mixed bed column packed with 0) to reduce the concentration of calcium and magnesium ions to 3/2 or less, and then 20/l of sodium isocyanurate dichloride and 150/l of sodium sulfate were added. did.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizer) Common to mother liquor and replenisher (unit: g) Formalin (3
7%) 1.2ml surfactant
064(C+otlz+-0+CHz
CHZO [11 ethylene diglycol
1. 0 Add water 1.0N
The concentrations of these samples obtained by the pH 5.0-7.0 treatment were measured, and the Dmin values measured using green light (G light) were read from the characteristic curves.

Next, as a standard bleaching solution that does not cause bleaching blade bleed, change to the following processing solution formulation, bleaching processing time is 390 seconds, processing temperature is 38°C, replenishing solution amount is 25mρ/35mm, sample length is 1m, and other conditions are as follows: The process was carried out without any changes.

(Standard bleach solution) Mother solution (6) Replenisher solution (g
) Ethylenediaminetetranodic acid ferric sodium trihydrate 100.0 12.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.09 Ammonium bromide 140.0 160.0
Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 relative 4, add OrnR water 1.0ffi 1.0f
fip H6,05,7 The density of the treated sample obtained using the above standard bleaching solution was similarly measured, and the Dmin value was read from the characteristic curve.

These obtained Dmin values were based on the Dmin value of the standard bleaching solution, and the difference between each sample, 80 mtn, was determined. In addition,
The Dmin value obtained using the standard bleaching solution at this time was 0.60.

Bleach blade Buri (△[]m1n) = (Dmin of each sample) (Dmin of standard bleaching solution)
The results are shown in Table 1.

Next, using the above sample, the increase in stain during sample storage after treatment was determined from the change in concentration of Dmin before and after the uncolored portion was stored under the following conditions.

0 Dark/moist heat conditions = 60° C. 170% RH 14 weeks Stin increase (80) - (Dmin after storage) (Mouth m1n before storage) The results are also shown in Table 1.

Incidentally, gas discharged from the exhaust port of the automatic processor was collected during the above continuous processing, and gas analysis of acid contained in this gas was performed by gas chromatography.

The results are also shown in Table 1.

1 92- From the results in the table above, processing N11 that satisfies the constituent requirements of the present invention
It can be seen that by carrying out step 2, the concentration of acid released into the room, which is related to environmental protection, is significantly reduced. Furthermore, it can be seen that it exhibits excellent effects on bleaching blade blur and staining during color image storage after processing.

Example 2 Using the sample prepared in Example 1, the same exposure as in Example 1 was given, and the acid in the composition of the bleach solution described in Example 1 was changed as shown in Table 2, and its concentration was changed. Mother liquor is 1.2 mol/l
Add the replenisher to 1.71 mol/2, adjust the pH of the mother liquor to 3.5 and the pH of the replenisher to 2.9 with aqueous ammonia (27%), and use it as a bleaching solution. did. The rest was carried out according to Example 1 without any changes.

After the continuous treatment, the concentration of the sample obtained by the treatment was measured, and the D+win value was determined from the characteristic curve.On the other hand, the DIllin value obtained using the standard bleaching solution of Example 1 was taken as the standard, and the concentration of the sample was measured. Standard fog was calculated in the same manner as above.

Furthermore, using the treated sample, the increase in staining during image storage after treatment was evaluated in the same manner as in Example 1. Furthermore, as shown in Example 1, the concentration of acid discharged into the room from the outlet of the automatic processor was also investigated.

These are summarized in Table 2.

94 From the results shown in the table above, it can be seen that the bleaching edge blur and stain are clearly lower than that of the corresponding monobasic or dibasic acid using the monocarboxylic acid using the non-dissociable hydrophilic substituent of the present invention.

Furthermore, the concentration of acid discharged from the automatic processor is extremely low, and there is almost no odor, which indicates that the acid is excellent in terms of environmental protection.

Example 3 Using sample 101 prepared in Example I, the same exposure as in Example 1 was applied, lactic acid was used as the acid used in the bleaching solution, and its concentration was changed as shown in Table 3, and further By changing the concentration, the pH of the bleaching solution was changed to mother liquor 6.0, replenisher 5.1; mother liquor 5.5, replenisher 4.7; mother liquor 4.5, replenisher 4.3;
Mother liquor 3.5, replenisher 3.0, mother liquor 3.0, replenisher 2.8
Adjust each using ammonia water (27%),
The rest was treated in the same manner as in Example 1. The acid concentration at the exhaust port of the automatic processor was measured in the same manner as in Example 1, but none was detected. Also, the same〈
Processing was carried out using the reference bleach solution described in Example 1.

These treated samples were densitometrically measured and the Dmin value measured in green light of the characteristic curve was read.

As in Example 1, these Ds+in values were determined based on the Dmin value obtained by treatment with the standard bleaching solution, and the bleaching blade blur was calculated for each sample for 80 minutes. These results are shown in Table 3.

7 From the results in Table 7, it can be seen that bleach blade smearing is reduced by increasing the acid concentration while keeping the pH of the bleaching solution constant. However, at an acid concentration of 2.0 mol/1 or more, the effect is saturated, and even if the concentration is increased, there is no effect of reducing bleaching fog, so the upper limit of the acid concentration is 2.0 mol/1.
It turns out that l is sufficient.

In addition, it can be seen that the bleach fog decreases when the pH value of the bleaching solution is lowered while the acid concentration is constant;
It can be seen that there is a large change between pH 0 and pH 5.5, and it is preferable to adjust the pH to 5.5 or lower.

Therefore, it can be seen from this example that the pH of the bleaching solution is preferably 5.5 or less, and the acid concentration is preferably as high as 0.2 mol/r or more.

Example 4 On a subbed cellulose triacetate film support,
Sample 401, which is a multilayer color light-sensitive material, was prepared by applying layers having the compositions shown below.

9- (Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrf units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 401) 1st layer (antihalation layer) Black colloidal silver 0.18 gelatin 1.00 2nd layer (intermediate layer) 2.5-G-mo-pentadecylhydroquinone 0,18EX-1
0,07 EX-30,02 EX-120,002 U-10,06 U-20,08 U-30,10 HBS-10,10 00 B5-2 Gelatin third layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ EX-2 EX-14 EX-10 B5-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye I Sensitizing dye ■ Sensitizing dye Dye Sensitive ■ EX-2 EX-14 0,02 0,90 0,25 0,25 X10-5 X1O-5 IXIO-' 0.160 0.1B5 0.020 0.060 0,80 1, 0 1 X 10-5 EX-3 EX-4 EX-2 B5-1 B5-2 Gelatin 6th layer (intermediate layer) EX-5 B5-1 Gelatin 7th layer (first green-sensitive emulsion layer) 02 0.050 0.015 0. 060 1, 20 ■, 60 4X10-' X1O-5 4X10-' 0.010 o, os.

O,097 0, 22 0, 10 1, 53 0,040 0,020 0,60 Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-6 X-15 X-1 X-7 X-8 B5-1 B5-3 gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye■ Sensitizing dye■ l-6 X-15 03- 0, 15 0, 15 Xl0-5 0XIO-' 8XlO-' 0.120 0.145 0.021 0.030 0.025 0.100 o,oi.

Ol　63 0,45 Xl0-5 Xl0-5 6XIO-' 0,047 0.047 X-8 E)'-7 HB S-1 B5-3 gelatin 9th layer (3rd green emulsion layer) Emulsion E Silver Sensitizing dye V 3゜ Sensitizing dye Vl &.

Sensitizing dye ■ 3° x-13 X-11 x-1 B5-1 B5-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver Silver X-5 B5-1 04 0.01B 0.026 0.160 0.008 0,50 1,2 5X10-'0XIO-'0XIO-' 0.015 0.100 0.025 0,25 0,10 1,40 0,05 0,08 0,03 Gelatin 11th layer ( 1st blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye ■ X-9 X-16 X-8 B5-1 Gelatin 12th layer (2nd blue-sensitive emulsion layer Emulsion G Sensitizing dye ■ X-9 X -16 10 Silver 0,45 2,lX10-' 0.070 0.093 0.007 0,05 0,70 Emulsion H silver 0.77 Sensitizing dye■ 2.2X10-'EX-
90,20 HBS-10,07 Gelatin 0.69 14th layer (first protective layer) Emulsion I Silver 0. 5U-40
,11 0-50,17 HBS-10,05 Gelatin 0.80 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.543-1
0.20 gelatin
1.10 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

　06 X 1 X death! H X-3 11 X-4 X H cbn+5(n) 09 X X death! 10- X 8 X ■ X 0 0 ■ Eχ 1 2 12 X 2 X 3 2 13- X 4 X 5 X 6 14 1 H 11 (tJ Ca h.

15- V B.S. ■ tricresyl phosphate B.S. hmm Petyl Phtalet to 16 Sensitizing dye I Sensitizing dye■ Sensitizing dye■ 17 Sensitizing dye V Sensitizing dye■ Sensitizing dye■ 18 Sensitizing dye■ S CH3 (■ CI+□ C11-502-CH2-CONII-CH2112 CI(-3o□-C11□-CONI(-C11219 The above photosensitive material was processed as follows.

Processing method step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 5 seconds 38°C 25% bleaching 10β 40 seconds 38°C 5ml l!
Bleach fixing 40 seconds 38°C [Fixing 40 seconds 38°C16d
i Washing with water (]) 330 seconds 38°C 2f washing
(2) 20 seconds 38°C 30m121 Stable 20 seconds 38°C20m1 21
゜Drying 1 minute 55°C
It was a countercurrent system from 2) to (1), and all the overflow of the bleaching solution was introduced into the bleach-fixing system.

Further, all the overflow liquid from water washing (1) was allowed to overflow to the fixing bath, and all the overflow liquid from the fixing bath was allowed to overflow to the bleach-fixing bath.

In the above process, the amount of fixer brought into the water washing process was 2ml per 1m length of the photosensitive material having a width of 35mm/m.

(Color developing solution) Same as the color developing solution of Example 1, bleaching solution) Mother liquor (8) 1.3-diaminopropanoic acid ferric ammonium acetate hydrate 144.0 Ammonium bromide 84.0 Ammonium nitrate 17.5 Glycolic acid 1.5 mo) Add water
1.01 pH' 3.5 (Fixer) Mother liquor (6) Ammonium thiosulfate aqueous solution (700g/l) 280mf ethylenediaminetetraacetic acid 12.6 Ammonium sulfite 27.5 Add water 11 pH 7,8 (Bleach-fixer) Replenish Liquid (6) 206.0 120.0 25.0 2.1 mol 1, Ol 2.9 Replenisher (g) 840ai! 8 82.5 1! 8.0 Mother liquor (6) 21 Ethylenediaminetetraacetic acid ferric ammonium dihydrate 1.3-Propanediaminetetraacetic acid 19,0 11,9 Ammonium sulfite 25.0 Ammonium thiosulfate aqueous solution (700g/i!,) 260ml
Ammonia water (27%) 6. (1+d
Add water 1.0! pH6
, 8 (Washing liquid) Same as the washing liquid of Example 1.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7%) 2. (ld Polyoxyethylene-P-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1. Oj! pH 5,0-8,
0 22 Next, the oxidizing agent of the bleach solution, 1.3-PDTA・Fe(I[
I) was changed as shown in Table 4, and the pH of the bleaching solution in part - was changed, and the treatment was carried out after continuous treatment without changing the other treatment methods.

The concentration of acid from the exhaust port of the automatic processor was measured in the same manner as in Example 1, but none was detected. Further, the density of the obtained treated sample was measured, and the Dmin value measured using green light was read from the characteristic curve.

On the other hand, sample 401 was prepared using the standard bleaching solution used in Example 1.
was treated according to the treatment method shown in Example 1, and the Dmin value was determined in the same manner as above. D+ of this standard bleach solution
Based on the win value, the bleaching blade burr and Δ(lain value) were calculated in the same manner as in Example 1.

The Dmin value using the standard bleaching solution at this time was 0.57. The results are shown in Table 4.

Subsequently, using the above-treated sample, a test was conducted for staining during image storage after processing under the same conditions as in Example 1, and staining was evaluated using the same method. These results are also shown in Table 4.

Further, samples uniformly exposed so as to have a gray density of 1.5 were processed in the same manner as above, and the amount of silver remaining in these samples was quantified by fluorescence XkfA method. These results are also shown in Table 4.

25 From the table, it is clear that an oxidizing agent with a redox potential of 130 mV or more, which is a preferred embodiment of the present invention, is used when the pH of the bleaching solution is low (pH
It can be seen that when used under 4,0) conditions, there is clearly less bleaching edge blur, less increase in staining during image storage after processing, and excellent desilvering. In contrast,
It can be seen that when using an oxidizing agent with a low redox potential, the bleaching effect is good regardless of the pH, but the staining and desilvering properties are poor. However, it is recognized that staining and desilvering properties can be improved by increasing the treatment time even at high pH.

Furthermore, it can be seen that for staining and desilvering properties, it is more preferable that the pH is lower, even if the oxidizing agent of the present invention has a high redox potential of 130 mV or more.

These facts show that by using an oxidizing agent with a high redox potential as a low pH bleaching solution, a rapid desilvering process can be performed without bleaching fog and with excellent stain and desilvering properties.

Example 5 Sample 501, which is a multilayer color brightening material, was prepared on a subbed cellulose triacetate film support 26 and each layer had the composition shown below.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rrr of silver for silver halide and colloidal silver, and the amount expressed in g/n (unit of silver) for coupler additives and gelatin. Regarding the sensitive dyes, the number of moles is expressed per mole of silver halide in the same amount.

1st layer (antihalation layer) Black colloid----1----0,
15 Gelatin −−−−−−−−−−−−−−−・−
----------m---1, 5E x M-8---
−−−〜 −−−0,08U■−1−−−−−−1−
1------0,03U V-2------・----
-------1--------0, 06SoIv
−2−−−−−−−−−−−−−0,08U V-3
−−−1−−−−−−−−−−−−−−−−0, 0
7Cp d -5----------11---
-=-6
5tJ V -1----------1--------
−−−−−−−0, 03U V −2−−−−−−−
-----1~---------0, 06U V -3
−−−−−−−−−−−−−−−−0, 07ExF−
1------------0,004
S o I v −2−−−−−−−−−−−−−
--0,07Cp d -5----1---------
-------6 29%, normal crystal, mixed twin grains, diameter/thickness ratio 2.5) Coated silver amount 0.5 Gelatin -------10, 8E x
S −1−−−−−−・−= 1.0XIO−'E
x S −2−−−−−−−−−−3, OX 10
−'E x S −3−=−−1−−−−−・−1−
--I X 10-'ExC-3・-・-・----1-
-------------0, 22E x C-4-
−−−−−−−−=−−−1−−−0, 02Cp d
−5−・−−−−−−−−−−3 Diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 1) Coated silver amount 0.7 Gelatin ---
-------1, 26E x S-1------
---1------------IX 10-'E
χS-2・−−1−・−1−−・−−−−−−−−−
-1-3X 10-'E x S-3---------
−〜−−−−−−−−−−−I X 10-5E x
C-3--------1--------------
--0, 33E x C-4--111----
--------0, OIE x Y -16-------
−−−−−−−−−−−− 0, OIE x
C-7−−−−=−−−−−−−1−−−−−−−
----------0, 04ExC-2--・----
------1-------------0, 08S o
l v −1−=−−−−−−−−−−−−−−〇 , 03Cp d−5−−−−−−−−−−−
----------5 Coefficient of variation in diameter 30%, twinned mixed particles, diameter/thickness ratio 2) 29 Coated silver amount 0.7 Gelatin 0, 8E x S -1------
--------------1-----I X I O-'E
x S-2−−−−−=−−−−−−−3X 10
- 'E x S -3------1----------
−−−−−−−・−I X 10− 'Ex C−
5-------------------------111-0, 05E x C-6-----
------ 0, 06S o I v-1----
---11-------------0, 15S o
I v −2=−−−−−−−−−−−−−0,
08Cp d −5−−1−−−−=−−−−−−3
X 10-5 6th layer (intermediate layer) Gelatin--1-・--1----1, OCp
d -5-111-------------1-4X 10-'Cp d-1---1-------
-----------0, 10Cp d -4-
------------------1-1, 23S
o l v-1-------0, 05Cp d
−3−−−1−−−−−−−−−1−−−−−0,2
5 Seventh layer (first green emulsion layer) Silver iodobromide emulsion (Agl 2 mol%, inner cylinder Agl type, equivalent sphere diameter 0.3 μm, spherical phase 30, coefficient of variation of equivalent diameter 28%, normal crystal, twin Crystal mixed particles, diameter/thickness ratio 2.5), -1------------- Coated silver amount 0.
30 Gelatin-------0, 4Ex
S-4----------1~-5XlO-
'E x S −6−−−−−−−−−・−−−−−0
, 3X 10-'E x S -5-----1---
-------------2X 10-'E x M
−9−−1−・−−−−−−1−−=−−−−−−−−
−−・−−−0,2E x Y −14−−−−1−
-------0, 03E x M-8-・----1-
−−・−−−−−1−−−−・−1−−−・−・ 0.
03S o I v -1---m---0, 2
Cp d-5-------2X 10-'8th
Layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (Agr 4 mol%, internal high Agl type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, mixed twin grains, diameter /thickness ratio 4) 111-----11----Coated silver N O16 gelatin
0, 8E x S-4------------
5X I O-'E x S -5--------1-
-2X 10- 'ExS-6--1 --0,3
×1O−4E x M−9−−−−−−−−−−
0,25E x M -8-111---0,03
EχM −10−−−−−−−−−−0, I 5E
x Y −14−−−−−−−−0, 04S o I
v −1−−−−−−−−0, 2Cp d −5
-------3x 10- '9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (8g 110 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30 %, normal crystal, mixed twin grains, diameter/thickness ratio 2.0) Coated silver amount 0.85 Gelatin ----- to 1--- 1. 0ExS-4
------2,0xlO-'E x S -5----
----2, OX I O-'E x S -6---
-・----0, 2X 10-'ExS-1----~
--3, OX 10-'E x M -12---
------0, 06E x M-13-・・----
1-------0, 02E x M -8-1~--
---0, 02S o I v-1----1----
-------0, 20S o l v -2------
~------0, 05Cp d -5------
-4X l O-'10th layer (yellow filter layer) Gelatin---------------=-=-11-
------0, 9 yellow colloidal silver--------
0,05Cp d −1−−−−−−−−m−−・−
0,2S o I v-1-------0,I
5Cp d -5---------4X 10
- '11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (8g 14 mol%, internal high Agl type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 15%, octahedral grains) ------m-Amount of coated silver 0. 4 Gelatin-----=-------・--------=
−−−−−・−1, OE x S−8−=−−−−−−
---1-----2X 10-'E x Y-I
G −−−−−−−−−−−−−−−−−−1−−
-----0, 9E x Y -14-----~--
---------- 0, 09S o I v -1
--------1-------0, 3Cp d -5--
-----=--------4 Coefficient of variation in diameter 25%, normal crystal, mixed twin grains, diameter/thickness ratio 4.5) Coated silver fi 0.5 Gelatin---111---0, 6E
x 5-8-1-----------IX 10-
'EχY −16−−−−−−−−−− 0, I
2S o I v −1−−−−−−−−1−−−
-〇, 04Cp d -5-----------・--
---1--------2X 10-' 13th layer (first protective layer) Fine grain silver iodobromide (average grain size 0.07 pm, Ag 11 mol%) ------ --1-0,2
Gelatin −−−−−−−−−−−−−−−−0, 8
U■−3−−−・−−−−−−−−−−1−−−−−−
-0, IU V -4--1・----1------
−−−−−−−−−−−0, IU V −5−−−−
-----111----0, 2134 So l v~3 ------- 0.04Cp
d -5---------3 Diameter 1.5μm) ------0.2Cp d
−5−−−−−−−−−−−−4X 10−′H−1
--------=----0, 4 In addition to the above-mentioned components, a surfactant was added as a coating aid to each layer. The sample prepared as described above was designated as sample 101.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

H3 H3 〇C112 C+ CIl 2 C-) 7- V olv Tricresyl diphosphate So]v ; Dibutyl phthalate olv ; Bis(2-ethylhexyl) phthalate Ex M 8 ; Shi! ExC 5: ゝC3H 1(t) ExC 6: 01) ExC 7: H2 xM 9: xM 10: 41 xM 12: xM 13: 42 ExY 16: pd 2: I'1N (IH 43 ExS 1: ExS 2: ExS 3: 44 ExS-4: ExS 5: ExS 6: 45 ExS-7: ExS CI+ □ co-so□-C1h-CONH-CIlzC11□-
CH-501-C112-CONH-C11□ 46 Cpd 4 : Cpd 5 : 1 The sample was cut and processed into 35 mm width, exposed to white light (light source color temperature 4800°K), and subjected to the following processing process. Processing was performed using a type automatic processor.

Treatment continued until the cumulative replenishment amount was twice the mother liquor volume in all treatment tanks.

The automatic developing machine has an agitation mechanism that squirts the processing liquid from a narrow rack in all tanks, and the bleach bath has a
It has the same aeration mechanism as described.

Processing method Processing time Processing temperature Replenishment ii” Ink capacity 3 minutes 5
Seconds 36.8'C25m1 20150 seconds 37
．． 5°c 5ml 54250 seconds 38°
C--! M! 147 Process color development bleaching bleaching fixing fixing 50 seconds 38°CI6mfl
50°Washing (1) 30 seconds 38°
C3N water washing (2) 20 seconds 38°C 34m
fl 31° stable 20 seconds 40°C
30 Storage 31 Drying 1 minute 30 minutes 55°C 9 Replenishment amount is the amount per 1.1 m length of 35 fence width.

9 All of the bleach solution overflows into the bleach-fix bath.

1 All of the fixer overflows into the bleach-fix bath.

9. The water washing is carried out in a counter-current manner from (2) to (] ), and all the overflow liquid from the water washing (1) is allowed to overflow into the fixing bath.

(Color developer) Mother solution (6) Replenisher (g
) Diethylenetriaminepentaacetic acid 2.2 2.21-Hydroxyethylian-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.948 Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-( Add N-ethyl-N β-hydroxyethylamine)-2-methylaniline sulfate solution H (bleaching solution) 1.3-diaminopropanoic acid Ferric acetate ammonium hydrate Ammonium nitrate Ammonium acid solution H 9 1,4 1,5■ 2.4 4.5 1, OI! .

10.05 Mother liquor (g) 44 4 17.5 1 3.3 6.4 1.0ffi 10.10 Replenisher (g) 49 'Mother liquor pH is 3° (bleach-fix solution) Ethylenediaminetetraacetic acid Ferric ammonium di water salt 1.3 It was set individually to be 3.

Diaminopropane mother liquor (gl) Replenisher (g) 18.6 Ammonium sulfite 17.3 Imidazole 25.9 Add water 1.0 pH 6,8 1 Bleach-fix solution by mixing overflow of bleach solution and overflow of fixer solution constitutes the liquid composition of

(Fixer) Mother solution (g) Replenisher (
6) Ammonium thiosulfate aqueous solution (70%) 280ml! 84
0ml ammonium sulfite 19.0 5
750 Ethylenediamine acetate 12.7 Midazole 28.5 Add water 1. Or pH 7,3 (Washing water) Same as the washing liquid in Example 1.

(Stabilizing solution) Same as the stabilizing solution of Example I.

8 85.5 1, Or 7.4 The concentration of the processing agent sample was measured, and the difference from the Dmin obtained by replacing only the bleaching solution with a reference bleaching solution (without bleaching blade blur) as in Example 1 was determined. Bleach blade value △Dmin
I asked for

Further, a sample uniformly exposed to a gray density of 2.0 was treated in the same manner, and the amount of residual silver in the sample after treatment was determined by fluorescent X-ray method.

Furthermore, in order to investigate the odor generated from the automatic developing solution, an automatic developing machine was installed in a 4 meter square room, and the odor in the room after processing during the day was investigated.

These results are shown in Table-5.

51 52 As shown in Table 5, the publicly used acetic acid is 1.3-
When propanediaminetetraacetic acid ferric complex ammonium salt is used in a bleaching solution that uses an oxidizing agent, increasing the acetic acid concentration reduces bleach blade blemish, but the odor caused by acetic acid becomes extremely unbearable. Put it away. On the other hand, when the glycolic acid according to the present invention is used, satisfactory performance is obtained, with no bleaching blade blemish and no odor generation.

It can be seen that when acetic acid is used in combination with glycolic acid, as long as the acetic acid concentration does not exceed 0.7 mol/l, the acetic acid odor in the environment is almost negligible, and the bleaching blade brittleness can be sufficiently suppressed.

Example 6 When processing method Nos. 501 to 509 described in Example 5 were carried out using the following color negative films, good effects similar to those in Example 5 could be obtained.

Fuji Color Super RII I 0053 (emulsion number 603022) Super HG200 (emulsion number 503011) Super HG400 (emulsion number 302020) Super HRII l 600 (emulsion number 701002) EALA (emulsion number 802013) Konica ■Konica Color GX11100 (emulsion number 712)
GX400 (emulsion number 861) Same as GX32
00 (Emulsion number 758) Eastman Kodak Company 00 for Kodacolor Gault (Emulsion number 819D31A) Same Gold 200 (Emulsion number 5096631) Same Gold 400 (Emulsion number 003D18A) 54 Godak Ector-1000 (Emulsion number 107D11A) (Effects of the invention ) By carrying out the present invention, a rapid desilvering process was achieved in which the problems associated with acid evaporation were improved, and furthermore, the bleaching edge blur and post-processing stain were also improved.

Claims (4)

[Claims] (1) In a method of processing an imagewise exposed silver halide color photographic light-sensitive material with a processing liquid having bleaching ability after color development, the processing liquid having bleaching ability contains no oxidizing agent and no hydrophobicity parameter. A method for processing a silver halide color photographic light-sensitive material, which comprises a monobasic carboxylic acid having at least one non-dissociable hydrophilic substituent as described below. (2) The method for processing a silver halide color photographic light-sensitive material according to claim (1), wherein the oxidizing agent of the processing solution having bleaching ability is an oxidizing agent having a redox potential of 130 mV or more. (3) The silver halide color photographic light-sensitive material according to claim (1), wherein the oxidizing agent of the processing solution having bleaching ability is an aminopolycarboxylic acid ferric complex salt having a redox potential of 130 mV or more. Processing method. (4) The pH of the processing liquid having bleaching ability is 2.5 or more.5.
5. The method for processing a silver halide color photographic material according to claim 1, wherein the silver halide color is 5 or less.