CA1282628C - Method for processing of color photographic elements - Google Patents

Abstract

SPECIFICATION

Title of the Invention METHOD FOR PROCESSING OF COLOR PHOTOGRAPHIC ELEMENTS

Abstract of the Disclosure A method for the processing of a silver halide color photographic element comprising imagewise exposing the element, color developing the exposed element, followed by de-silvering, characterized in that the de-silvering step comprises processing the developed element in a bleaching bath containing an aminopolycarboxylic acid ferric ion complex salt and subsequently in a blixing bath containing an aminopolycarboxylic acid ferric ion complex salt and a fixing agent.

Description

BACXGRO D OF THE INVE~TION

(1) - IBLD OF TH33 INVENTION
Thi3 invention relates to a method for processing o~
imagewise exposed color photographic light-Qensitive elements containing ~ilver halide thereinafter, referred to a~ "color photographic elemen~s") and more particula~ly, to an improved pho~ographic process whlch enables sufficient de~silvering in a shortened time and produce~ good guality color rep~oduct~ons.
`

(2) DESC~IPTION OF T~ PRIOR ART
.
Ba~i~ processes for processing color pho~ographic elements generally include a color development step and de-lS silvering step, ~n the color development, image~ise exposedsilver halide is reduced by a color developing agent to ~orm metallic sllver and the oxidized color dev.eloping agen~ reacts with a coupler (or dye forming agen~) to form a color image.
In the subsequent de-silvering step, the metallic silver 20; formed in the color .development i5 oxidized by an oxidizing agent (generally called ~a bleaching agentn) and ~he oxidized silver i~ then dissolved by a silver iron complexing agent generally called a fixing agent. This de~ilvering step essent~ally leave~ a dye image on the color photographic 25 ~ elements.

The de-~ilvering step i3 done wi~h either a bleaching bath containing a bleaching agent followed by a fixing bath ~ ~ i - 2 - . ~ ,1 , ~,, ,~

containing a fixing agen~ or a single bleach-fixing bath (or blixing bath) containing both bleaching and fixing agents.
In addition to these basic steps, the actual procedures of color development processes include various additional steps such as hardening step, stopping step stabilizing s~ep and washing step, so as to obtain a dye image having a better pho~ographic and physical quality and a longer stability of the dye image.
Ferricyanides, dichromates, ferri chloride, aminopolycarboxylic acid ferric ion complex salts and persulfates are generally known as the bleaching agent.
Howeverj ferricyanides and dichromates are liable to cause environmental pollution and the use thereof requires special equipment for the treatment of such chemicals. Ferric chloride has various problems in practical use. For example, it forms ferric hydroxide and produces stains in a subsequent washing step. ~Persu'lfates have disadvantages in that they are very weak in bleaching power and therefore require an `~ extremely long time for bleachin~. In this connection, there ~0 has been proposed a method for improving the bleaching power of persulfates by using them together with a ' bleach accelerator. ~owever, this method is not practical because the use and storage of persulfates are controlled by Fire -Prevention Law and consequently require special facilities.
Aminopolycarboxylic acid f'erric ion complex salts (or ferric salts of an aminopolycarboxyli¢ acid), particularly ethylenediaminetetraacetic acid ferric ion complex salt (or ferric salts of ethylenediaminetetraaacetic acid) are the bleaching agents most widely used at present because, unlike persulfates, they have few problems regarding environmental pollution and storage. However, the bleaching power of the aminopolycarboxylic acid erric ion complex salts i5 not always sufficient. The complex salts may attain the desired de-silvering when they are used to bleach or bleach-fix a low-speed silver halide color photographic element mainly containing silver chlorobromide emulsion, while the complex salts cannot achieve sufficient de-silvering or they need a long time for bleaching when they are used to process a high-speed color photographic element mainly containing silver bromoiodide or silver bromochloroiodide emulsion and having been spectrally-sensi~ized, especially a color reversal photographic material or a color negative photographic material for photographing containing an emulsion of high ~. .
silver content.
For example, the bleaching time of the photographic color negative ligh~sensitive material in the bleach bath of the aminopolycarboxylic acid ferric ion complex salt is at least four minutes and it is necessary to take troublesome precautions such as pH control or aeration in order to maintain the bleaching power at the desired level. Even if such precautions are taken, it is not rare that de-silvering is not carried out sufficiently~
For the purpose of completa de-silvering, it is further necessary to treat the element in a fixing bath for at ~ ~ 8~

least three minutes following the bleaching bath.
Accordingly, there is a strong need to shorten the time for de-silvering.
For accelerating the de-silvering, there i5 known a S bleach-fixing solution, as disclosed in German Patent 866, 605, which contains both aminopolycarboxylic acid ferric ion complex salt and thiosulfate. However, the bleachins power of this solution is very weak because the blixing solution contains aminopolycarboxylic acid ferric ion complex salt which itself is weak in oxidizing power (or bleaching power) and thiosulfate which has a reducing power. It is, therefore, very difficult for this blixing solution to attain the de-silvering of a photographic color light-sensitive material of high speed and high silver con~ent and consequently this lS blixing solution cannot be employed for practical useO Many attempts have been made to ovexcome these disadvantages of tbe blixing solution. Examples of such attempts include the addition of iodides or bromides thereto as disclosed in British Patent 926, 569 or Japanese Patent Publication No.11,854/1978 (U.S.P. 4,040,837) and the incorporation of high concentration of aminopolycarboxylic acid ferric ion complex sal~ thereto using triethanolamine as disclosed in Japanese Patent Public Disclosure No.g5,834/1973. However, none of these methods has sufficient effect for practical use.
In addition to its poor de-silvering ability, the blixing solution has another serious drawback in that it reduces the cyan dye formed by color development to the leuco _ 5 _ . . . . - . . , dye and consequently interferes with color reproduction. It is known that this drawback ~an be reduced by elevating the pH
value of the blixing solution as disclosed in U.S.P.

3,773,510. This method is, however, almost useless from a S practical point of view because the elevation of the pH value resul~s in weakening of the bleaching power of the solution.
U.S.P. 3,189,452 discloses a method wherein, after blixing, the leuco dye is oxidized to the cyan dye by a ferricyanide bleaching solution. But ~he use of the ferricyanide brings about the problPm of environmental pollution and the bleaching after the blixing has almost no effect on the decrease in the remaining silver content.
As an alternative method for increasing the bleaching power of the aminopolycarboxylic acid ferric ion complex salt, there has been proposed a method wherein various bleaching accelerators are added to the bleaching bath, the blixing bath or ~he preceding bath.
Examples of such accelerators include various mercapto compounds as disclosed in U.S.P. 3,893,858, British Pa~.
138,842 and Japanese Patent Public Disclosure No.141,623/1978;
compounds having disulfide linkage as disclosed in Japanese Patent Public Disclosure No. 95,630/1978 (U.S.P. 4,169,733);
thiazolidine deriva~ives as disclosed in Japanese Patent Publication No.9,854/1978; isothiourea derivatives as disclosed in Japanese Patent Public Disclosure No.94,927/1978 ~U.S.P. 4,144,068); thiourea derivatives as disclosed in Japanese Patent Publication Nos. 8506/1970 (U~S.P. 3,617,283) .

~8~

and 26,586/1974 ~U.S.P. 3,809,563); thioamide compounds as disclosed in Japanese Patent Public Disclosure No.42,349/1974 (GB 1,394,357); and, dithiocarbamic acid sal~s as disclosed in Japanese Patent Public Disclosure No.26,506/1980.

s Although some of these accelerators do in fact have a bleach accelerating effect, the effect is, however, not sufficient to meet the ~eed for shortening of the processing time.

SUMMARY OF T E INVENTION
A first object of this invention is to provide a method for the processing of a color photographic element, especially one of high-speed and high silver content, which enables sufficient de-silvering of the element in a shortened time and produces good quality color reproductions.

. A second object of this invention is to provide a method for th processing of a color photographic element, ` which gives rise to few or no problems of environmental pollution or storage o chemicals to be used therein so that the method can easily be put to practical use.
The inventors of this invention found that the objects of this invention can be attained ~y ~ubjecting an imagewise exposed color photographic element to a color development, processing the developed element in a bleaching bath containing an aminopolycarboxylic acid ferric ion complex salt, followed by a blixing bath containing an , ~.

8~6~3 aminopolycarboxylic acid ferric ion complex salt and a fixing agent. In other words, ~he inven~ors found that by using the bleaching bath containing the aminopolycarboxylic a~id ferric ion complex salt, which is weak in the ~leaching power, followed by the bLixing bath containing the aminopolycarboxylic acid ferric ion complex salt and the fixing agent i~ is possible to ensure de-silvering of the photographic element in a shorter time than in prior art processes wherein bleaching and fixing baths are used, and to minimize the likelihood of the formation of the leuco form of cyan dye, which has been one of the problems in the use of the blixing bath. These are unexpected advantages since said blixing bath is weak in bleaching power and would ordinarily be considered incapable of easily processing a color lS photographic element particularly one of high sensitivity and high silver content.
As mention~d above, the bleaching power of the aminopolycarboxylic acid ferric ion complex salt is not always sufficient and becomes weaker in the blixing bath in which the complex salt and the fixing agent coexist. Therefore, de-silvering of a color ~hotographic element of high-speed and high silver content has always been done by keeping the coLor photographic element in a bleaching bath for a long time, and thereaftPr subjecting it to a separate fixiny bath. In this method, a water washing s~ep is usually required between the bleaching and the ~ixing steps in order to avoid the incorporation of the bleaching solution into the fixing bath ~x~
to thereby interfere wi~h the formation of ~he leuco form of cyan dye, or elevation of the pH value of the fixing bath is required to avoid the formation of leuço form o~ cyan dye, as disclosed in Japanese Patent Public Disclosure No.70533/1982.
U.S.P. 3,189,452 discloses de-silvering in a blixing solution and it also describes that a bleach bath containing a ferricyanide having a strong bleaching power is required after the blixing so that the leuco form of the cyan dye is converted to the colored form of the cyan dye.
From the common knowledge set out above it is not possible to imagine or anticipate the advantages of the process of this invention which comprises processing the photographic element in the bleaching bath for a shortened time, followed by the blixing bath, in view of de-silvering ability and Xormation of leuco form.
Fur~her the inventors found that the color photographic element containing the cyan dye-forming coupler o~ the formula (I) or (II) produces good quality color reproductions when it is processed by the process of this invention wherein the time for de-silvering is shortened as much as possible:

, .

X~

o~
R.3 ~,Nl:~

cor~ I
Z

t ~ ) N HC o R, 4 IJ
~ .
~2 ;

:

, - ', ' ' ~ : '' ' ;' ' :, - . , ' . .
:. ,., :
, wherein Rl, R2 and R4 represent substituted or unsubstituted aliphatic, aryl or heterocyclic group, R3 and R6 represent hydrogen atom, halogen atom, subs~ituted or unsubstituted aliphatic, aryl or acylamino group, or non-metallic atom group which forms a nitrogen-containing five or six membered riny, R5 represents substituted or unsubstituted alkyl group (preferably having at least two carbon atoms), Zl and Z2 represent hydrogen atom or a group which can be released at the time of the coupling reaction with a color developing agent, and n represents 0 or 1.
When the cyan couplers of the above formulas are used, good quality color reproductions can be attained without softening of the gradation of the cyan image even when the bleaching is carried out for a shortened time.

DETAILED DESCRIPTION OF THE INVENTION
The aminopolycarboxylic acid ferric ion complex salts used as a bleaching agent both in the bleaching bath and in the blixing bath are a complex of ferric ion and an aminopolycarboxylic acid or salt thereof. The aminopolycarboxylic acid ferric ion complex salts used in the flixing bath may be the same as or different from those used in the bleaching bath.
Typical examples of the aminopolycarboxylic acid and salt thereof include:

, ~ X 6~

A-l ethylenediaminetetraaceti~ acid A 2 disodium ethylenediaminetetraacetate A-3 diammonium ethylenediaminetetraacetate A-4 tetra (trimethylammonium) ethylenediaminetetra-acetate A-5 tetrapotassium ethylenediaminetetraacetate A-6 tetrasodium ethylenediaminetetraacetate A-7 trisodium ethylenediaminetetraacetate A-8 diethylenetriaminepentaacetic acid A-9 pentasodium diethylenetriaminepentaacetate A-10 ethylenediamine-N (~-oxyethyl)-N,N',N'-triacetic acid A-ll trisodium ethylenediamine-N-(~-oxyethyl)-N 9 N'oN'~ triacetate A-12 triammonium ethylendiamine-N~ oxyethyl)-N,N',N'-triacetate ~-13 propylenediaminetetraacetic acid A-14 disodium propylenediaminetetraacetate A-15 nitrilotriacetic acid A-16 trisodium nitrilotriacetate A-17 cyclohexanediaminetetraacetic acid A-18 disodium cyclohexanediaminetetraacetate A-l9 iminodiacetic acid A-20 dihydroxyethylglycine A-21 ethyletherdiaminetetraacetic acid A-22 glycole~herdiaminetetra~cetic acid A-23 ethylenediaminetetrapropionic acid .

.:
' ' It is ~o be understood that these compounds are described only for the purpose of illustration and therefore other aminopolycarboxylic acids can also be used in this invention.
SAmong these illustrated compounds, A-l, A-2, A-3, A-8, A-17, A-l~ and A-19 are particularly preferred.
The aminopolycarboxylic acid ferric ion complex salts may be used in the form of complex salt or they may be formed iQ a solution by mixing a ferric salt such as ferric sulfate, 10ferric chloride, ferric nitrate, ferric ammonium sulfate etc.
with the aminopolycarboxylic acid. The complex salt may be used alone or in combination with one or more of other complex salts. Nhen the complex salt is formed in a solution, one or more aminopolycarboxylic acids and one or more ferric salts lSmay be used. In all cases, aminopolycarboxylic acid may be used in excess of the amount necessary to form the ferric lon complex salt.
The bleaching solution or the blixing solution containing the ferric ion complex salt may contain other 20metallic ion complex salts than iron, such as cobalt, copper, etc.
The bleaching solutions used in this invention may contain, in addition to the bleaching agents and the compounds mentioned above, re-halogenating agents such as bromides, for 25example, potassium bromide, sodium bromide, ammonium bromide, or chlorides, for example, potassium chloride, sodium chloride, ammonium chloride. Any of the addenda used in ~ ~ ~2~
conventional bleaching solutions may be added to the bleaching solutions used in this invention including inorganic acids, organic acids and ~alts thereof having the capacity for buffering a pH, for example, nitrates such as sodium nitrate, S ammonium nitrate, boric acid, bora~, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid and the like.
The amount of the bleaching agents con~ained in one liter of the bleaching solution used in this invention is 0.1 to 1 mole, preferably 0.2 to 0.5 mole. The pH of the bleaching bath is adjusted to 4.0 to 8.0, preferably 5.0 to The amount of the bleaching agents contained in one lS liter of the blixing solution used in this invention is 0.05 to 0.5 mole, preferably 0.1 to 0.3 mole.
The inventors further found that the effect of the addition of at least one bleach accelerator selected from the compounds having mercapto group or disulfide linkage, isothiourea derivatives and thiazolidine derivatives to the bleaching bath used in this invention is superior to the e~fect of the addition of the same accelerator to the bleaching bath used in the prior art bleaching and fixing steps. In addition, they also found that the bleach accelerating effect is achieved and maintained for much longer than is the effect obtained in the prior art de-silvering process comprising the bleaching bath and the fixing bath.

~x~

The fixing agents which may be used in the blixing bath used in this invention include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates such as 5sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, thiourea, thioether, ekc. The amount of the fixing agents contained in one liter of the blixing solution is 0.3 to 3 moles, preferably 0.5 to 2 moles.
In addition to the bleaching agents and the fixlng 10agents described above, any of the addenda may be added to the blixing solution used in this invention, if required.
For example, one or more pH adjusting agents may be added such as sulfites, e.g. sodium sulfite, ammonium sulfite, etc., boric acid, borax, sodium hydroxide, potassium 15hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, acetic acid, and sodium acetate. Various antifoaming agents, surface-active agents, alkali metal halides such as potassium iodide, potassium bromide, ammonium ` bromide, etc., ammonium halides, hydroxylamine, hydrazine or 20addition products of aldehyde with bisulfite may also be contained in the blixing solution used in this invention.
The pH of blixing solution used in this invention is adjusted to 5 to 8, preerably 6 to 7.5.
Preferably, the time for bleaching in` this invention 25is 20 seconds to 4 minutes. The time is more preferably 20 seconds to 2 minu~es, where a color photographic element containing the cyan dye-forming couplers of the formula (I) or - 15 ~

(II) is processed and the bleach accelerating agent of the formulas (III) to ~IX) described a~ter is used, while it is preferably 1 to 4 minu~es where the accelerating agent is not used. The bleaching time is preferably 40 seconds to 2 minutes where a color photographic ~lement not con~aining the cyan dye-forming couplers of the formula (I) or (II) is processed and the bleach accelerating agent of the formulas (III) to (IX) is used, while it is preferably l.S ~o 4 minu~es where the accelerating agent is not used.
The time for blixing is preferably 1 to 5 minutes, more preferably 1.5 to 3.5 minutes. Less than 20 seconds of bleaching time results in poor de-silvering even i~ the blixing time is extended, while less than one minute of blixing time also results in poor de-silvering even if the bleaching time is extended.
In this invention, a water washing step may be provided between the bleaching and the blixing steps. The advantages of this inven~ion are not impaired even when a water wash step in which very small amount of water is ~0 supplied is used.
Preferably, a replenisher is introduced into the blixing bath in this invention. The replenisher contains essential components such as the bleaching agent or the fixing agent. A replenisher containing the fixing agent is advantageously used.
When the processing is in progress, the overflow solution, which flows out of the bleaching bath when the 8',,~ 8 bleaching replenisher is added thereto, may be introduced into the blixing bath. This is very economical because the level of the bleaching agen~ in the blixing bath is maintained by the introduc~ion of the overflow solution from the preceding bleaching bath. From the stand point of the prevention of environmental pollution, it is desirable to decrease the amount of the waste liquid of the photographic process, which hàs high biochemical oxygen demand (BOD) and high chemical oxygen demand tCOD). The decrease in the amoun~ of the waste liquid by the use of the overflow solution makes the photographic process more economical.
In the process wherein the replenisher is introduced into the blixing bath, the overflow solution from the bleaching bath, which is discharged in ~he prior art process, is introduced into the blixing bath. As a result, the overflow solution functions as a solvent which dilutes the replenisher component to the desired level. Accordingly, the replenisher may be supplied to the blixing bath in the form of a` concentrated liquid, which results in a decrease in the amount of was e liquid~
As described earlier, the incorporation of the bleaching solution into the fixing bath brings a~out the formation of the leuco form of cyan dye and significantly damages photographic properties and therefore, it is usual to 2S provide a watex washing step between the bleaching ~tep and the ixing s~ep so that the incorporation is prevented.
NEQCOLOR CHEMISTRY FOR C-41 NEGATIVES, First Wash (published ~ 28 by L.B. RUSSELL C~EM~CALS, U.S.A.~ describes that insufficient water washing brings about the problems just mentioned above and therefore a water wash is very important.
Japanese Patent Public Disclosure No.70533/1982 describes that it is necessary to raise the pH of the bleaching bath when the water washing step is omitted so that the formation of the leuco form of cyan dye and the degradation of ~he bleaching solution are prevented. Thus, the incorporation of the bleaching solution into the fixing solution has been considered very disadvantageous. It is therefore apparent that this invention in which the overflow solution from the bleaching batb is mixed with the fixing agent to form the blixing solu~ion is quite different from or contrary to the prior art concept.
In this invention, the amount of the bleaching bath overflow solution introduced to the blixing bath and the amount of the bleaching agent - containing solution supplied to the blixing bath are adjusted so that the concentrations of the bleaching agent and the fixing agent in the blixing bath are maintained within the range described earlier. The amounts depend on the concentration of the bleaching a~ent in the overflow solution to be introduced and the concentration of the fixing agent to be supplied and they are preferably 150 m~ to 900 m~ per one square meter of the photographic element to be processed.
In this invention, the replenisher supplied to the blixing bath may contain any of the addenda wbich can be added .. . .
' ' . ' ' ,' ' ' : . ' .~ ' '~

~'~ 8Z ~'~ 8 to the fixing bath, for example, conventional fixing agents such as ammonium thiosul~ate, sodium thiosulfate, etc., sulfites, bisulfites, buf~ers and chelating agents. The concentration of each of these components in the replenisher may be adjusted so as to form a blixing solution of the desired concentration when the replenisher is mixed with the overflow solution from the bleaching bath and it may be higher than the concentration in the replenisher to be supplied to the conventional fixing bath. As a result, it is possible to decrease the amount of waste liquid and consequently to lower the cost for the treatment of the waste liquid.
The concentration of the fixing agent contained in the replenisher supplied to the blixing bath is preferably 0.5 to 4 mole~, more preferably 1 to 3 mole/~.
The pH of the replenisher is preferably 6 to 10, more preferably 7 to 9. The replenisher may contain the aminopolycarboxylic acid ferric ion complex salts, ammonium halides or alkali metal halides such as ammonium bromide, sodium bromide, sodium iodide and the like.
In this invention, the overflow solution from the bleaching bath may be introduced into the blixing bath directly, for example, by connecting the overflow tube on the bleaching bath to the blixing bath, or indirectly, for example, by storing the overflow solution in a container, mixing it with a fixing agent-containing solution and then introducing the mixed solution into the blixing bath or introducing the stored overflow solution and the fixing agent into the blixing bath separately.

. . :
~ ~ `

6~

The cyan dye-forming couplers of the formula (I) or ~II) used in this invention will now be explained in detail.
In the formulas, Rl, R2 and R4 represent aliphatic groups having 1 to 32 carbon atoms such as methyl, butyl/
tridecyl, cyclohexyl and allyl; aryl group such as phenyl and naphthyl; or heterocyclic group such as 2-pyridyl, 2-imidazolyl, 2~furyl and 6-quinolyl; and the aliphatic, the aryl and the heterocyclic groups may be substituted by one or more groups selected from alkyl, aryl, heterocyclic, alkoxy such as methoxy and 2-methoxyethoxy, aryloxy such as 2,4~di-tert-amylphenoxy, 2-chlorophenoxy and 4~cyanophenoxy, alkenyloxy such as 2-propenyloxy, acyl such as acetyl and benzoyl, ester such as butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl and toluensulfonyl, amido such as acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamido and bu~ylsulfamoyl, sulfamido such as dipropylsulfamoylamino, imido such as succinimido and hydantoinyl, ureido such as phenylureido and dimethylureido, aliphatic or aromatic sulfonyl such a~ methanesulfonyl and phenylsulfonyl, aliphatic or aromatic thio such as ethylthio and phenylthio, hydroxy, cyano, carboxy, nitro, sulfo, halogen atoms and the like.
In the formula (I), R3 represents hydrogen atom, halogen atom, aliphatic group, aryl group, acylamino group or a group of non-metallic atoms which form a nitrogen-containing five or six membered ring together with R2. These groups may be substitu~ed by one or more substituting groups as defined previously with respect to Rl.
In the formula (I), n represents 0 or 1.
In the formula (II), R5 represents substituted or S unsubstituted alkyl having at leas~ two carbon atoms such as ethyl, propyl, butyl, pentadecyl, tert-butyl, cyclohexyl, cyclohexylmethyl, phenylthiomethyl, dodecyloxyphenylthio-methyl, butaneamidomethyl and methoxymethyl.
In the formula (I), R6 represen~s hydrogen atom, halogen atom, aliphatic group, aryl group, or acylamino group.
In the formulas (I) and (II), Zl and Z2 each represent hydrogen atom or a coupling off group, for example, halogen atom such as fluorine, chlorine and bromine atoms, alkoxy such as ethoxy, dodecylocy, methoxyethylcarbamolymethoxy, carboxypropyloxy and methylsulfonylethoxy, aryloxy such as 4-chlorophenoxy, 4-methoxyphenoxy and 4-carboxyphenoxy, acyloxy ~uch as acetoxy, tetradecanoyloxy and benzoyloxy, sulfonyloxy such as methanesulfonyloxy and toluenesulfonyloxy, amido such as dichloroacetylamino, heptafluorobutyrylamino, methane-sulfonylamino and toluenesulfonylamino, alkoxycarbonyloxy suchas ethoxycarbonyloxy and benzyloxycarbonyloxy, aryloxycarbonyloxy such as phenoxycarhonyloxy, aliphatic or aromatic thio such as ethylthio, .phenylthio and tetrazolylthio, imido such as succinimido and hydantoinyl, and aromatic azo such as phenylazo. These coupling off groups may contain a photographically useful group.
In the formula (I), Rl is pre~erably aryl or `', : .

;
, , ~ ~ ~2 ~2 ~

heterocyclic group, and more preferably aryl group substituted by halogen atom, alkyl, alkoxy, aryloxy, acylamino, acyl, carbamoyl, sulfonamida, sulfamoyl, sulfonyl, sulfamido oxycarbonyl or cyano group~
In the formula (I), if R2 and R3 do not form a ring toge~her, R2 is preferably sub~tituted or unsubsti~uted alkyl or aryl, and more preferably alkyl substituted by substituted aryloxy, and R3 is preferably hydrogen atom~
In the formula (II), R4 is preferably substituted or unsubstituted alkyl or aryl, and more preferably alkyl substituted by substituted aryloxy.
In the formula (II), R5 is preferably alkyl having 2 to lS carbon atoms or methyl having a substituting group which has at least one carbon atom, which substituting group is preferably arylthio, alkylthio, acylamino, aryloxy or alkyloxy.
In the formula (II), R5 is preferably alkyl having 2 to 15 carbon atoms and more preferably alkyl having 2 to 4 càrbon atoms.
In the formula (II), R6 is preferably hydrogen atom or halogen atom and more preferably chlorine atom or fluorine atom.
In the formulas (I) and (II), Zl and Z~ are each hydrogen atom, halogen atom, alkoxy, aryloxy, acyloxy or sulfonamido group.
In the formula (II), Z2 is preferably halogen and more preferably chlorine or fluorine atom.

- 2~ -~ ~2~jqæs In the formula (I~, if n is zero, Z2 is preferably halogen and more preferably chlorine or fluorine atom.
The cyan dye-~orming couplers of the formula (I) or (II) are usually incorporated in silver halide emulsion layers, particularly a red sensitive emulsion layerO The amount of the coupler incorporated is 2 x 10-3 to 5 x 1o-l mole/mole Ag, and preferably 1 x 1o-2 to 5 x 10-1 mole/mole Ag.

The cyan dye-forming couplers of the formulas (I) and (II) may easily be prepared according to the methodst as described in U.S.P. Nos. 3,772,002; 4,334,001; g,327,173; and 4,427,767.
Typical illustrative examples of the cyan dye-forming couplers of the formulas (I) and (II) include the following tG
which this invention is not restric ed:

~ .

.
;,' .' æ~

( C--~ ) o~
k~ C OC 3 1 2H~i ,~
(t)C ~ ~OC~CON~I

(t3C 5 H 1 1 C~--2 ) OH
~ M~C O--~) C,~9~302NH~:)C~CON~I

C~

(~
tC-3 ) ~Cl2~Z5 COlY~I C~
\~=J C~
tC3H7 )~302NH

, 2~

C~
OEI
1 2H2 a ~ N~IC ~!~ k ~ H g ~OCHCON~

C--0~

C6 ~, 5 1~ ~) c--6 9 C~

Cl2H2s ,~ ~, ce .
. , .

~'~8~6'~8 C--7 ) ,~, C~OC~s NC~OCtICON~l ( C~

,~ OC~, ~OCHCONH
F
C~

C~

~i~C3H7 5)2 N4~0C~CON~I
W C~

~a~8~2~D~3 ( C~ / O ) :E F
OH \_~
,~3,N HCO~

~3C5Hg l~OC~CONH
\=< ~b .

.
( C~
O ~ .

~t~5H~ l~Ob~lCON~ I N~302 C~
\=~ , C~

( C--~ a ) N ~C 0 ~C~7~oC~cO~H I NH~30;~C2~40 C~
~_ ~ Cl : ' ~ ' ' i .

~2 C~ 3 ) 0~1 I 1 2~2 5 ,J~ NH~ 2 C 2 H5 NC~OC HC O N~
~ ce ( C--/ 4 ) N ~IC 1~3 (t)C ~ ~9 C
~7~ 1 ~ N~lS02 C~3 C ,H~aO~OC KCONH
CC

( ~--J ~ ) NHCO~
(t)C~Hg ~ ~ ~ NH~3O2C~3 HQ~/ \~OC HCO NH

.
.

- 2~ -.

~ c~
OH
(~)C 8 H 1 7 ~ HC 0~

C~C ONH ¦ NH ~ 0 2 ( ~ 3 ~ C~
- OC~Hg C~ 7 ) 2~2 5 ~1~ NHCO~-~y~ C
~)_~OCHCON~l I

(t)~ 3 ( C~

C~LIg (t)CsH~ O C~I CC) NH o ~t,lC ~ H~
-r ~
~C~I3 _ ;~9 _ :- . .

. .

.

C_J ~ ) N~

1 2H5 ~) ce NH~302~(;ff, (tlC~Hll~ OC~CON~

tt)C5Hl 1 ( C--2 o ) ()H
,~N.YCO~

(~)CsHI I~OC~:lCOI`li~/~ NH~02Cz~OCH~

~t)C5 ( C--2 J ~

5~ N~C~ Ct)CS ~11 o NH~o2~23~D~(b~4 ( C--2 ~ 3 ~3, NUC (: ~

H I N~30~Cl~33 ( C~
C~
. 3 ~NHCO~) 1) N~ - NH;302 ~CI 2~2 s ~1 2~ 5 N~"NIICOC~CN

CZ

, "
.
:. ' ` ' ' ` :

æ~

2 ~ ) F
C ~ H ~_ H
~ , ( C--2 ~ ) CH~" _~ IC,~{

~ N~COC: t3C5H~

' 2 7 ) 2~5 o~N~,NHCOCHO~NH~30,C4H~, ' , .. .. ,; ~-.

826~ ~3 C--~ 8 ) OH

~1!1~CON~CN

(t)Cs~ VC~CON~

(t)C5 ~t)C~H, ~OCHCONH

(t)C 8 H,~

( C--3 ~ ) 0~1 -,~ N

~t)C8~l 7~0C~ICONH

(~C 8 IIl, , , .
,.

z~

t ~--3 ~ 3 ~t)C 5Hll~O C}IC O N H
~t)C5 ( C~3 2 O H _~

'~Oa~~
(i)CS~ll~O(~ 0N~l 3 (t)CSH~, a ( C --3 3 ) ( )2N(C2~;) 2 8~17 kl) (t)C8~1~0CHC~

ce 2~3 C~

C4 ~ ~3/ NHC OM~CN

(t)C5~l l~OC~ICONH

~t)C 5 C--3 ~ ) ~i I ~ 7 ,~, N~CONH~;~7 (t)C8Hl~OC~( ON-H

)(8Hl~

IC~4 )~ CN

(t)C5~ l~OC~C~ONH o (t)C,H~

OC~ 3 :

.

' ' ~z~

3 7 ) ~, N~C O NH ~r~

~t~C~ O

(t)C8Hl 7 ~1 '`~

~t,~C 8 ~1 7 ( ~--3 ~ ) 1)~

$3 (t~C~Hl ,~OC~CON~l (t)c 8 ~ t 7 t C~3 ,~3, N HC () N

(t?C ~ ~O~:ICON~l ,=~ .
(~)C5H~ 1 ( C~ 4' 0 ) C~3 0~1 ~
~3, NHC Oy \~:

~0 C HC O~H

(t~C

) f. U
e cc ~3~NHCOCHl~Cs~

c2~s (lt~C5 ~, ` :

.
.

..

.: , ) C~ ~3, H i ~(t)C5 C~s (t)C5 ~1 1 ce ( C--4~3 ) C~
,NHCOCHO~_(t)C6 C,~Ig~ ~)C~
ce , ~, N~IC OC uo~')C 5 ~1 1 ~t)C4~9 ~J (t)Cs ` --3~ --.
,. ..
.

s ~

C H 3 ~3~ N~ Oc H~t)c s C~

6 ) o~ ~ C2Hs ~ ICOCH~ 7 C,, 5~31 ~J (t~C 5 H
C~ .

7 ) ct~3~N~lCoc}lo-~tk 1`

(t~ 5 ~1 1 `

3x6~Z~3 ( C~

ce ~3~N HC ( ) CHO~ )C 5 C3F7cO~c~z C~

C~

C2~5 HC~ S)CsH~ s C~3 OCH2 ~ (t)C 5 , tC--so) a ~3~N~COC~(t)Cs~

C 2 H5 (~C 5 ~;

~2 C~2 , ~L~ 82 ~ ~

The bleaching accelerators will now be explained in detail.
The bleaching accelerators which may be incorporated in the bleaching ba~h used in this invention are any of compounds which have bleach accelerating effect and are selected from compounds having mercapto group or disulfide linkage, thiazolidine derivatives or isothiourea derivatives.
The accelerators are preferably selected from the compounds of the formulas (III) to (IX).
` 10 C l~L

Rl ~
/N--( CH2 )n~~

wherein Rl and R2 may be the same or dife~ent and represent h.ydrogen atom, substituted or unsubstituted lower alkyl preferably baving l to S carbon atoms, particularly methyl, ethyl and propyl; or acyl preferably having l to 3 carbon atoms, such as acetyl and propionyl, and n is l, 2 or 3.
Rl and R2 may form a ring togetherO
Rl and R2 are preferably substituted or unsubstituted lower alkyl.
Examples of the substituting groups which R1 and R2 contain include hydroxyl, carboxyl, sulfo and amino groups.

1~8Z~2~i3 ~3 l ~ N - ~ C ~2 9 ~ - 8 ~ 2 wherein R3 and ~4 are the same as described previously regarding Rl and R2 of the formula (I), and n is 1, 2 or 3.
R3 and R4 may form a ring together.
R3 and R4 are preferably substituted or unsubstituted lower alkyl group~
Examples of the substituting groups which R3 and R4 contain include hydroxyl, carboxyl, sul~o and amino group~

~:

, ~ . ' , ' , ~ ' , , 32~28 .~ y N -- N
Il 11 C C
/ \ /\
~s ~) N ~ N
1~ 11 C
/ ~ /\
Rs N ~I
I
H

N = N
N N
~/ R
~H

.

.

~, . , , ~
.

, ?/L~82~fæ,8 wherein R5 represents hydrogen atom, halogen atom such as chlorine or bromine, amino, substituted or unsubstituted lower alkyl preferably having 1 to 5 carbon atoms, particularly methyl, ethyl and propyl, and alkyl-containing amino such as me~hylamino, ethylamino, dimethylamino and diethylamino groups.
Examples of the substituting groups which Rs contain5 include hydroxyl, carboxyl, sulfo and amino groups.

/

wberein R6 and R7 may be the same or different and each represents hydr.ogen àtom, substituted or unsubstituted alkyl, preferably lower alkyl such as methyl, ethyl and propyl, subs~ituted or unsubsti~uted phenyl or substituted or ~0 unsubstituted heterocyclic, more specifically heterocyclic having one or more hetero atoms such as nitrogen, oxygen and sulfur atoms, for example pyridinP ring, thiophene ring, thiazolidine ring, benzoxazole ring, benzotriazole ring, thiazole ring and imidazole ring.
R8 represents hydrogen atom or substituted or unsubstituted lower alkyl preferably having 1 to 3 carbon atoms, such as methyl and ethyl.

., ~ .

~ ~ 8~

Examples of the substituents which ~6, R7 or R8 may contain include hydroxyl, carboxyl, sulfo, amino and lower alkyl groups, Rg represents hydrogen atom or a carboxyl group.

S ( ~) N~1 o C ~ C ~
N ~1 1 R ~ 2 L0 wherein Rlo~ Rll and ~12 may be the same or different and each represents hydrogen atom or lower alkyl preferably having 1 to 3 carbon atoms, such as methyl and ethyl.
Rlo and Rll or R12 may form a ring together.
X represents amino, sulfonic or carboxyl group which may contain one or more substituents, for example, lower alkyl such as methyl and acetoxyalkyl such as acetoxymethyl.
Rlo, Rll and R12 are most preferably hydrogen atom, methyl or ethyl group, and X is most preferably amino or dialkylamino group.
Typical illustrative examples of the compounds represented by the formulas (III) to (IX) include the following:

. . .
. :'. ' ' ' , ~
:. ~ .. . .
~,. .... . .
, ( m ) \N~ 2 ) 2--SH
/

I3C \
( C~2 3 2 -~3H
~3 C
~ .
( m ) ~ (3) ~N -( C~2 ) 2--8 Hs ~ 2 m ) (4) ~N--C H ;~
~ ,~
~3 ~
~ m )-~s) : \/N~ 2 ~ 2~3 . ~3~0~ ::

HOOC~2 C
~N--(C H2 ) 2--~3C

, :
.

.

'. ' .

8~

~ m 3 - (7) r~3 \
~N--~ CH2 ) ;~ ~H
HOC ~2 C H2 ( m ) ~8) C~3 ~2C~ C~2 ,~N--( C~2 ) 2 ~ ~{3 ~3 ( ) 2 C~ 2 (9) O,~N~tC~2 )2 ~3C
~N--( CH2 ) 2--~
\ ~3C ~2 ( IY )--(2) H5C2~
~N--( C~ ) 2--~3 Hsc2 J2 - . ,. .. . :: . ~ .

.
.: ...

: .
, .:

~8~
3) / ~3 ~ N--C H 2--( N ) ~ (4) , / ~ ~ ~ .
~ C H 2 3 2 ~ t \~I3COC~ ~2 t ~i~2 C ~
~N--~ C~ 2 ) 2--~3t ( ~ 3 (~) OH
~3c~ 2 --C~2--~2 \ ~l3cc~lcH:2 12 OH
.

, ( N ) ~7) C~3 ~02C~2~2 `~ \
lY--CH2-C~2-s1 C~3 /2 t ~ ~ (8) ( C~ C ~2- ~t t ~ )--(g) ( Ca--CH2--C~2--37 (10 O N--C .~,--C ~ 2 :--49--::

: ' ' . ~ .
.
'' ~` , . .
. .
, z~

( ~ ) ~1) N -- N
Il 11 C
H

) `(23 N -- N
1: C
/\ ~\
H 3 C: 8 ( Y)--t3) N ~ N
` 11 11 H ;~
.

)--~4~
N -- N

C :
/ \3/ \~

. -- so--.
' ~ .

' .

N ~ N
Il 11 ~. C
/ \ /\
I

(2) . . N ~ N
11 ~1 C
/ \/\
NH2 N ~{

3~
N - N
Il . Il C, C
/ \ / \
. C H 3 N .

( t~ ) Sl) N -- I C~13 N N ~ C~2 ) 2 ~\
~/ CH3 8~

2~

~T a ~
N ~ H 2 3 2 1~ 2 o ~1~

.
~ ~ ) ~tl~
~ 2 C
3 C~2 1I n ,~
r~2 ~--N

( ~)--(2) EIz C ~N/ \~
H
3) H 2 C ~ N C IL, H

, ` 52-:, , ' ': . . ' .: .
.

- ~ ,, ' ' ;. ' z~
4) ~2 C \C ~

El2 C ~ N C~ 3 5) S
~2 C ~ CE~;~
C -~ -- C
2 --N H H \l~C~2 H

6) C--~\

C~2 ~)OC--C--N/
i ~ .
( ~ )--(1) ~3C ~ ~ 1J--~3 ~tCH2)2 ~-C~
H3 C ~ NH--CH 3 a ~ Cl : . '' , ~ ' .
: .' . ~ .

~3C \ 1~--C2~5 N--( C~2 ~ 2~ C
H3 C N~C 2 ~5 ~ 2 Hc~

( K)--~3) H3 ~ \ ~ N--~ C~2 ) 2 CH3 N~ ~ CH,. )--8--C
H3C \ NH~( C~2 ) 2~E~3 C ~ 4) ~3 ~ 3 N ~C~I2~2--~--C
C \
5) C~3~ C~232\ ,~N~
/N -CC~)2--9--C\ O a ~1~ -CH3 ~32 t C~2 ) 2 P~2. .

. .
.
:
- : . . ' . ,: ., - . .

t ~ )--lo) C~3 ~3 2 (~2C) 2 \ ~
~2~2~ C\ q~ 2HCt ~13 C ~H;~

7) 3Cl-tH2C)2 \ ~N~l /N ~C~2)2 H3C NH;~ 2~~

O

~OOC--t C~ 2--~3 C ~
\ MH2 lg~
N~l H~OC--C~12--9--C ~
\ N~2 --s5--, . . .
. ~ ,., . ~ ~. , .
:

6~1 ) ~(10) NH
HC~3~--~C~2~a~ ~\

~ ~--t H3 C \ ~ ~ C~l~
/N--~ C~I2~ 2--~--C ~ I ~ ~ 2 ~1 All the compounds of the formulas. (III) to (IX) may be prepared by well known methods. For example, the method for preparation of the compounds of the formula (III) is desc~ibed ` in U.S.P. 4,285,98, G. Schwar~enbach et al., ~elv. Chim.
Acta., 38, 1147 (19555), and R.O. Clinton et al., 3.Am. Chem.
SOC., 70, 950 ~1948); that of the formula (IV) is described in Japanese Patent Public Disclosure No. 95630/1978; that of the formulas (V) and (VI) i5 described in Japanese Patent Public Disclosure No. 52534/1979; that of the formula (VII) is described in Japanese Patent Public Disclosure Mos.
68568/1976, 70763/1976 and 50169/1978; that of the formula (VIII) is described in ~apanese Patent Publication No~

- , - ~
- :
. .
. .
.
, .

~82~Z8 9854/1978 and Japanese Patent Public Disclosure No.
214855/1984 (U.S.P. 4,508,817); and that o~ the formula (IX) is described in Japanese ~atent Public Disclosure No.
94927/1978.
The amount of the compounds having mercapto group or disulfide linkage, thiazoline derivatives or isothiourea derivatives contained in the bleaching solution used in this invention depends on the kind of photographic elements to be processed, temperature at which the elements are processed, time requïred for the desired processing and other conditions but it is suitably 1 x 10-5 to lo-l mole/æ, and preferably 1 x 10-4 to 5 x lQ~2 mole/~l .
These compounds are usually dis~olved in a solvent such as water, alkali, organic acids, organic solvents and the like be~ore they are added to the bleaching solution.
Alternatively~ they may be added directly, that is, in the form of powder, to the bleaching solution, which does not have any influence on tbe bleach accelerating effect.
` ` Any of the silver halides such as silver bromide, silver bromoiodide, silver bromochloroiodide, silver chlorobromide, silver chloride can be used in the photographic emulsion layers of the color photographic elements used in this invention, especially, color photographic elements using the silver halide emulsions which contain silver iodide in the amount of preferaby up to lS mole %, particularly 2 to 12 mole .

x~z~

The emulsions used in the photographic elements processed by this invention can be prepared by well known methods as described in P. Glafkides, Chimie et Physique Photographique (Paul Montel, 19671, G.F. Duffin, Photographic S Emulsion Chemistry (Th~ Focal Press, 1966), V.L. Zelikman et al, or Making and Coa~ing Photographic Emulsio~ (The Focal Press, 1964).
Cadmiu~ salts, zinc salts, lead salts, thallium salts, iridium sal~s or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, or the like may be allowed to coexist during the forma~ion or physical ripening of silver halide qrains.
Usually, the silver halide emulsions are chemically sensitized, although they can be used without chemical sensitization~ that is, in the. form of the so-called primitive emulsion. The chemical sensitiza~ion can be. effected by the methods as described in the book written by. Glafkides or Zelikman et al, or H. Frieser Die Grundlagen der ~ Photographischen Prozesse mit Silberhalogeniden (Akademische Verlagsgesellschaft, 1968). Namely, sulfur sensitization using a sulfur-containing compound which can react with silver ion or active gelatin, reduction sensitization using a reducing compound, noble metal sensitization using noble metals such as gold can be used alone or in a combination of 2S two or more of them.~ Examples of the sulfur sensitizers include thiosulfates, thioureas, thiazoles, rhodanines and the like. Examples of the reduction sensitizers include stannous .

.' , . : ' ' ' ' ' ' ' , ~:

~ 2 ~

saltst amines, hydrazine derivatives, formamidinesulfinic acid silana compounds and the like~ Examples of noble metal sensitizers include complex salts of noble metals of Group VIII of the periodic table, such as gold, platinum, iridium and palladium.
The photographic emulsions may be spectrally sensitized with methine dyes or the like. E~amples o~ useful dyes for thi~ purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Especially useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
In addition to ~he light-sensitive silver halide emulsion layers described above, emulsion layers of substantially non light-sensitive silver halide fine grains may be provided so as to improve graininess or sharpness or to achieve other objects; Such substantially non light-sensitive emulsion layer~ can be provided over a light-sensitive silver `~ halide emulsion layer or between the light-sensitive silver halide emulsion lay~r and a colloidal silver layer (yellow filter layer or halation prevent;ng Iayer~.
The photographic elements used in this invention may contain polyalkyleneoxides or, ether, ester or amine derivatives thereof, ~hioether compounds, thiomorpholines, quaternary ammonium salts, urethane derivatives, urea derivatives, imidazole derivativest 3-pyrazolidone derivatives GZ~3 or the like to increase sensitivity, or contrast, or to accelerate development.
As a binder for photographic emulsion layers or other layers, gelatin is advantageously used, although other hydrophilic colloids can also be used.
The photographic elements used in this invention may contain various compounds as antifoggants or stabilizers7 Examples of these antifoggants or stabilizers include azoles such as benzothlazolium salts, nitroindazoles, triazoles, ben~otriazoles and benzimidazoles (particulary nitro or halogen substituted); he~erocycli~ mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto-benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly l-phenyl-5-mercaptotetrazole) and mercaptopyrimidines; the heterocyclic mercapto compounds having a hydrophilic group such as carboxyl and sulfone groups; thioketo compounds such as oxazolinethione; azaindenes such ~as tetraazaindenes (particularly 4-hydroxy substituted ` (1,3,3a,7) tetraazaindenes); benzenethiosulfonic acids;
benzenesulfinic acids; and the like.
The photographic elements used in this invention may contain inorganic or organic hardeners in the photographic emulsion layers and/or other layers. Examples of these ~ hardeners include chromium compounds such as chromium alum and chromium acetate, aldehydes such as formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds such as dimethylol urea and methyloldimethyl-hydantoin, dioxane derivatives such as 60 ~

~#X62~3 2,3-dihydroxydioxane, active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-S-triazine and 1,3-vinylsulfonyl-2-propanol, active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine, mucohalogenic acids such as mucochloric acid and mucophenoxychloric acid. These hardners may be used alone or in a combination.
The photographic emulsion layers or other layers of the photographic element used in this invention may contain various surface active agents as coating auxiliary agents, anti-static agents, or agents for improving sliding property, emulsifiability, dispersibility, anti-adhesion and photographic properties, for example for the purposes of development acceleration, high contrast and sensitization.
The photographic emulsion layers of the photographic lS elements used in this invention may contain, in addition to the cyan couplers described above, color-forming couplers which can form color by oxidative coupling with a primary aromatic amine developing agent such as phenylenediamine : derivative~ and aminophenol derivatives to form a colored dye ~0 in a color development step. Examples of these couplers include known cyan couplers such as phenolic couplers and naphtholic couplers, magenta couplers such as -S-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers and open-chain acylacetonitril couplers, and yellow couplers uch as acylacetamide couplers (e.g.
benzoylacetanilide~ and pivaloylacetoanilides). The cyan dye-forming couplers of the formula (I) or (II) can be used in a z~

combination with known phenolic or naphtholic cyan couplers and they can also be used in the polymerized form. Of these couplers, non-diffusible couplers having a hydrophobic group called ballast group are desirable. The couplers may be of 5either 4-equivalent type or 2-equivalent type to silver ion.
Colored couplers having color-correcting effec~ or couplers capable of releasing a development inhibitor up~n development (the so-called DIR couplers) may also be used. In addition to DIR couplers, colorless DIR coupling compounds which form a 10colorlesq coupling reaction product and release a development inhibitor or DIR redox compounds may also be incorporated.
The photographic elements used in this invention may contain a developing agent, typical examples of which are described in Research Disclosure, VolO 176, p.29 (1978), 15"Developing agents"~
The photographic elements used in this invention may contain dyes in the photographic emulsion layers or other layers as a filter dye or for the purposes of the prevention ` of irradiation or other objects. Examples of the dyes are 20described in Rese~rch Disclosure, Vol. 17~, pages 25 to 26, (1978), "Absorbin~ and filter dyes".
The photographic elements used in this invention may also contain antistatic agents, plasticizers, matting agents, lubricating agents, ultra violet light absorbers, fluorescent 25whitening agents, air fog preventing agents and the like, as described in Resèarch Disclosure, Vol. 176 (1978), pages 22 to 27.

-~2 -~ ~ 8Z ~Z ~
The silver halide emulsion layers and/or other layers are coa~ed on a support. The coating methods as described in Research Disclosure, Vol. 176, pages 27 to 28, (1978) "Coating Procedures" may be used.
S The process of this invention can advantageously be applied to the processing of multilayer negative color light-sensi~ive materials which contain incorporated color-forming couplers or color light-sensitive ma~erials for reversal color processing and fur~her, color X-ray light-sensitive materials, monolayer special color light-sensitive materials or color light-sensitive materials which contain incorporated black-and-white developing agents such as 3 pyrazolidones as described in U.S.P. Nos. 2,751,297 and 3,902,905, Japanese Patent Public Disclosure Nos. 64339/1~81, 85748/1981 and 85749/1981 and incorporated precursors of color developing agents as described in U.S.P. Nos. 2,478,400, 3,342,597, 3,342,599, 3,719,492 and 4,214,047 and Japanese Patent Public Disclosure No. 135~28/1978. The process of this invention can be effected even if these couplers are incorporated in the developing solution.
The process of this invention may advantageously be applied to color photographic elements which contain a large amount of silver, for example, at least 3 g/m2, preferably 3 to 15 g/m2 of silver.
Primary aromatic amine color developing agents contained in the color developing solution used in this invention include those widely used in various color ~8~
photographic processes. These developing agents include aminophenol and p-phenylenediamine derivatives. These compounds are usually used in the form of salts, ~or example, hydrochlorides or sulfates which are more s~able than the free form thereof. These compounds are usually used in a concentration of about 0.1 g to about 30 9, preferably about 1 9 to about 15 9 per one liter of the color developing solution.
Examples of aminophenol developing agents include o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene and 2-oxy-3-amino-1,4-dimethyl-benzene.
Especially useful primary aromatic amine color developing agents are N-dialkyl-p-phenylenediamine compounds, alkyl and phenyl groups of which may or may not be substituted. Useful examples of these compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-` phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-~ dodecylamino)-toluene, N-ethyl-N-~-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-~-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, and 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.
`In addition to the primary aromatic amine color developing agents described above, the alkaline color developing solution may optionally contain various components usually added to conventional color developing solutions, for ~8~2~

example, alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyana~es, alkali metal halides, benzylalcohol, water so~eners and thickening agents. The pH
S of the color developing solution is usually at least 7, most typically about 9 to about 13.
The process of this invention may be applied ~o color reversal processing. Black-and-whi~e developing solutions used in the color reversal processing include those called black-and-whi~e firs~ developing solutions used in reversal processing of color photographic elements and those used in processing of black-and-white light-sensitive materials. The black-and-white developing solutions used in this invention may contain various well known additives which are usually added to conventional black-and-white developing solutions.
Examples of typical additiYes include developing agents such as l~phenyl-3-pyrazoiidone, Me~ol (Registered trademark) and hydroquinone, preservatives such as sulfites, ` alkali accelerators such as sodium hydroxide, sodium carbonate and potassium carbonate, inorganic or organic inhibitors such as 2-methylbenzimidazole and methylbenzthiazole, water softners such as polyphosphates, and development inhibitors such as a small amount of iodides or mercapto compounds.
The process of this invention comprises the color development, the bleaching and the blixing steps described earlier. After the blixing, water washing and stabilization steps are usually provided. However, a simpler process in z~

which after the blixing, the stabiliæation is carried out without substan~ial water washing can also be used in the process of this invention.
Washing water used in the water washing step may contain known additives, if necessary. Examples of the additives include chelating agents ~uch as inorganic phosphoric acid, aminopolycarboxylic acid and organic phosphoric acid, germicides for the inhibition of propagation o~ bacteria or Algae, hardening agents such as magnesium salts and aluminum salts, and surface active agents for the pr~vention of unevenness. The compounds as described in LoE~
West, "Water Quality Criteria "Pho~O Sci. and Eng., vol. g No.6, page 34~ -359 (1965) can also be incorporated. ~wo or more washing baths can be used, if required and multi-stage countercurrent water wash (for example, 2 to 9 stages~ can also be used to save washing water.
A solution in which a color image is stabilized is used as a stabilizer in the stabilizing step. Examples of the ` stabilizer include a buffer solution having a pH of 3 to 6 and an aldehyde-containing solution, e.g. formalin. The stabilizer may contain, if necessary, fluorescent wnitening agents, chelating agents, germicides, hardening agents and surface active agents.
Two or more stabilizing baths can be u~ed, if necessary and multi-stage countercurrent water wash (e.g. 2 to 9 stages) can also be used to save the s~abilizing solu~ion and further, water wash can be eliminated.

, .

:

~2~i2~
Example l Multilayer color negative films were made on different pieces of a triacetylcellulose film support. The composition of each of the layers was as follows 1st layer: Antihalation layer Gelatin layer which contains black colloidal silver.
2nd layer: Interlayer Gelatin layer which contains an emulsified dispersion of 2,5-di-t octylhydroquinone.
3rd layer: Low speed red-sensitive emulsion layer Silver bromoiodide emulsion .. .....the amount o (silver iodide: 5 mole %1 silver coated l.6 g/m2 lS Sensitizing dye I .... per l mole of silver 6 x 10-5 mole 5ensitizing dye II O~ per l mole of silver l~5 x 10-5 mole Coupler .... per l mole of ~as described in Table l) silver 0.04 mole Coupler EX-l .... per ~ mole of silver 0.003 mole ~ .

2~3 Coupler EX-2 .... per 1 mole of silver 0.0006 mole 4th layer: High speed red-sensitive emulsion layer Silver bromoiodide .... the amount of (silver iodide: 10 mole %) silver coated 1~4 g/m2 Sensitizing dye I ... O per 1 mole of silver 3 x io-5 mole Sensitizing dye II .. ~. per 1 mole of silver 1.2 ~ 10-5 mole Coupler .... per 1 mole of (as described in Table 1) silver 0.02 mole Coupler EX~ per 1 mole of silver ; 0.0016 mole 5th layer: In~rlayer The same as tha~ of the 2nd layer 6th layer: how speed green-sensitive emulsion layer Monodlsperse silver .... the amount of ` bromoiodide emulsion silver coated (silver iodide: 4 mole %) 1.2 g/m2 . 68 . , , .
. ' ; , ~
, - . ' , ;

Z~3 Se~sitizing dye III .... per 1 mole of silver 3 x 10-5 mole Sensitizing dye IV O~ per 1 mole of silver 1 x 10-5 mole Coupler EX-3 .... per 1 mole of silver ` 0.05 mole Coupler EX-4 .... per 1 mole of silver 0.0015 mole Coupl~r EX-2 .... per 1 mole of silver 0.0015 mole.
7th layer: High speed green~sensitlve emulsion layer Silver bromoiodide emulsion .. ......the amount of ~silver iodide: 10 mole %) silver coated ` 1.3 g~m3 Sensitizing dye III .... per 1 mole of silver . 2.5 x 10 5 mole Sensitizing dye IV .... per 1 mole of silver ~ 0.~ x 10-5 mole V~6Z~

Coupler EX-5 .... per 1 mole of s i lver O . 017 mole Coupler EX-4 .... per 1 mole of silver 0.003 mole Coupler EX-6 .... per 1 mole of silver 0.003 mole 8th layer: Yellow f ilter layer Gelatin layer comprising yellow colloidal ~silv3e and an emulsified dispersion of 2,5-di-t-octylhydroquinone in an aqueous gelatin solution.
9th layer: Low speed blue-sensitive emulsion layer silver bromoiodide emul-qion ......... the amount of ~silver iodide: 6 mole %) silver Goated ' ' O . 0'1 g/m2 Coupler EX-7 .... per 1 mole of ~ silver 0.25 mole Coupler EX-2 ... O per 1 mole of silve~
0.015 mole l~th layer: High speed blu~-sensitive emulsion layer Silver bromoiodide emulsion ................ ...the amount of (silver iodide: 6 mole %) silver coated 0~6 g/m2 .

Coupler EX-7 ...................... per 1 mole of silver 0.06 mole 11th layer: First protective layer Silver bromoiodide ................ the amount of (silver iodide 1 mole %, silver coated average grain size 0.07 )1 ) 0,5 g Gelatin layer containing an emulsified dispersion of an ul~raviolet light absorbing agent W -1 12th layer: Second Gelatin layer containing trimethyl methacrylate particles of about 1.5 microns in diameter.

Gelatin hardening agent H-l and/or surface active agent were added to each of the layers in addition to the compositions ~e~cribed above.
.

< The compounds used to prepare the compositions >
Sensitizing dye I:
anhydro-5rsl-dichloro-3~3l-di-(r-sulfopropyl)-9-~0 ethylthiacarbocyanine-hydroxide, pyridinium salt Sensitizing dye II:
anhydro-9-ethyl-3~3~-di-(r-sulfopropyl)-4~5~4l~5l-dibenzothiacarbocyanine-hydroxide, triethylamine salt Sensitizlng dye III:
anhydro-9-ethyl-5,5'-dich}oro-3,3'~ddi-(y-sulfopropyl) oxacarbocyanine, sodium salt ' i28 Sensitizing dye IV:
anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di (r-sulfopropyl)ethoxy~ethyl~ imidazolo-carbocyaninehydroxide, sodium salt :

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The color negative films thus prepared were exposed to tungsten light at 25 cms (the color temperaturei of which had been adjusted to 4800~ through a fil~er~ thirough a wedge, 5 followed by color development at 38C as follows:

Process 1 (Comparative process) Color development 3 min. 15 sec.
Bleaching As described in Table 1 Fixing As described in Table 1 Washing 3 min. 15 sec.
Stabilizing 1 min. 5 sec.
Process 2 tComparative process) Color development 3 min. 15 sec.
Blixing As described in Table 1 Washing 3 min. 15 sec.
Stabilizing 1 mln. 5 sec.
Process 3 ~Process of this invention) Color development 3 min. 15 sec.
20` Bleaching As described in Table 1 Blixing As described in Table 1 Washing 3 min. 15 secO
Stabilizing 1 min. 5 sec.
The composition of each of the processing solutions 25 used in the steps described above was as ~ollows:

Color developing solution Trisodium nitrilotriacetate 1.9 g .~ .

æ~
Sodium sulfite 4 g Potassium carbonate 30.0 9 Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulEate 2.4 g 4-tN-ethyl-N-~-hydroxyethylamino)- 4,5 9 2-methylaniline sulfate Water to 1.0 ~
pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid, 100.0 g ferric ammonium salt Ethylenediaminetetraace~ic acid, 8.0 g disodium salt Ammonium bromide 150.0 g Ammonia water 128%) 7.0 m~
Water to l.OL
pH 6,0 Fixing solution Sodium tetrapolyphosphate 2.0 g Sodium sulfate 4.0 g A~ueous ammonium thiosulfate solution 175.0 m~
~70%) Sodium bisulfite 4.6 g Water to 1.0~ pH 6~6 Blixing solution Ethylenediaminetetraacetic acid, ferric 100~0 9 Ammonium salt Ethylenediaminetetraacetic acid, 4.0 9 disodium salt Aqueous ammonium thiosulfate solution (70%) 175.0 m~
Sodium sulfite 4-5 g Ammonia water 15 m Water to 1.0~
pH 6~8 Stabilizing solution Formalin (40%) 8.0 mQ

(Polyoxyethylene para- 5.0 m~
monononylphenyl ether, 0.3 g/~

Water to 1.0~

The minimum density, gradation and relative sensitivity of each of the film samples thus processed were measured. An amount of residual silver in the area of maximum color density was measured by X-ray fluorescence analysis.
Separately, the same film sample~ were processed by another process, FUJI COLOR PROCESS CN-16 of FUJI PHOTO FILM
CO,, ~TD. (color development, 3 min. 15 sec.; bleaching, 6 min. 30 sec.; washiny, 2 min. 10 sec.; fixing, 4 min. 20 sec.; washing, 3 min. 15 sec.; stabilizing, l min. 5 sec., followed by drying. Processing temperature was 3~C), followed by the measurement of the minimum density, gradation ale~lo~o tr~Je ~n~flC

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and relative sensitivity of the processed samples. The results were compared with those obtained by the processes 1 to 3 described earlier.
The comparative results are shown in Table 1 by the differences between the specific values obtained by the processes 1 to 3 and those obtained by the control ~CN-16 process). ~inimum density values were omitted because they were not signiflcan~ly dif~eren Table 1 shows that the greater the absolute numerical values of gradation and relative sensitivi~y become, that is, the greater the differences from the results of ~he control process, the worse the photographic properties get~
The relative sensitivity and yradation were determined as follows:
lS Relative sensitivity:
The difference between the minimum density and the density at an exposure value which corresponds on the characteristic curve, to a density of 0.2 above the ` minimum density of the control sample.
Gradation:
The diference between the density at the exposure value as defined above and the density at an exposure value greater by 1.5 of logarithm than the exposure value as defined above.
Comparative compounds A, B and C as shown in Table 1 are cyan dye-forming couplers of the following formulas.

.Z8 Comparative compound.,~, ( ~ 5 ~

~,CONH~CH2)30~Cs~l l(t) Comparative compouna g 0~
~,CO~

C~2 C ~2 ~ C~lC O 0~
C 1 2 H ~ 5 (n) Comparative compound C

~,NHCOCHO~C,HIl(t) ~ ~ ~Z 6~ ~

Table 1 clearly shows that the process of this invention enables de-silvering to a sufficient level for practical use in such a time, during which neither the .bleaching - fixing process (Comparative sample Nos. 1 to 3) nor the single blixing process (Comparative sample Nos. 4 to 6) enables de silvering sufficiently. As seen from the differences in the relative sensitivity and gradation between the control and the examples, the process of this invention gives good quality photographic reproductions without the formation of leuco form of cyan dye. Even in this invention, when the time for de-silvering is ~hortened to 4 minutes (bleaching 1 min. 30 sec.; blixing 2 min~ 30 sec.), the gradation and relative sensitivity of Red-sensitive layer are reduced on rare occasion as seen from the sample Nos. 13 a~d 14. However, it can generally be said that the process of this invention can be used in combination wi~h the cya~ dye-forming rouplers of the formulas I and II to ensure both de-silvering and exc~llent photographic reproductions.

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Example 2 The color negative film sample No.l as described in Table 1 (cyan dye-forming couplers used are Comparative compounds A and B) was cut into a 35 mm-wide film which in turn was .exposed through a wedge in a similar manner to that of Example 1, ~ollowed by the processing according to the Process CN-16 using an automatic developing processor to prepare a control sample. Separately, the color negative film sample No.l was sub~ected to the Process 1 or 2 as described in Table 2 using the automatic developing processor.

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It should be noted that the comparison was made under the condition that ~he time for bleaching in Process 1 that is, 5 minutes is equal ~o the total time for ~leaching and blixing in Process 2 as shown in Table 2.
The color negative films (35 mm - wide, 100 m - long per day) were used for outdoor photography, and were then subjected ~o the processings o~ Processes 1 and 2.
Separately, the same color negative films were subjected to wedge-exposure once a day, followed by the processings of Processesl and 2. Theseprocedureswerecarriedoutforten successive days.
Compositions of the solutio~s and the replenishers used in Processes 1 and 2 are as follows:

Color developing solution Initial solution Replenisher Sodium nitrilotriacetate . 1.0 g 1.1 g Sodium sulfite 4.0 g 4-4 g Potassium carbonate 30.0 g 32.0 g Potassium bromide 1.4 g 0.7 g ~ydroxylamine sulfate 2.4 g 2.6 g 4-(N-ethyl-N-~-hydroxyethylamino -2-methylaniline sulfate 4.5 g 5.0 g Wa~er to 1.0 Q 1.0 ~
pH 10.0 pH 10~2 Bleaching solution Initlalsolution Replenisher Ammonium bromide 160 g 176 g Ethylenediaminetetraacetic acid, sodium ferric salt 130 g 143 g Ethylenediaminetetraacetic acid, disodium salt 10 g 11.5 g Ammonia water (28%) 7 m? 4 m~
Wàter to 1 1 1 ~
pH 6.0 pH 5.7 .
Blixing solution Initial solution Reple~isher Ethylenediaminetetraacetic acid, sodium ferric salt 70 g 70 g Ethylenediaminetetraacetic acid, disodium salt 4.0 g 4.0 g Aqueous ammonium thiosulfate solution ~70%) 175 m Q 200 m ~
Sodium sulfate 4.5 g 4-5 9 Ammonia water (28%) 12 m Q 13 m~
Wa~er ~o 1 ~
pH 6.8 pH 7.0 ~ 2 Fixing solution Initial solution Replenisher Sodium tetrapolyphosphate 2.0 9 2.0 g Sodium sulfite 4.0 g 5.0 g Aqueous ammonium thiosulfate solutton (70%~ 175 m ~ 200 m Q
Sodium bisulfite 4.6 g 5 g Water to 1.~
pH 606 pH 6.6 Stabilizing solution Initial solution Re~Ien~he, Formalin (40%) 5 m~ 7 m~
(polyoxyethylene para- 5 m~ 7 m~
monononylphenyL ether, 0.3 g/
water to , 1 Q 1 æ

.

.

Table 3 Processing Steps Amount of Replenisher per 1 meter of film Process 1 Process 2 (Comparative~ (This invention) Color development 40 m~ 40 m~
Bleaching 15 m~ 15 m~
Fixing 40 m~ -Blixing - . 40 m~
Stabilizing 40 m~ 40 m~

The amoun~ of residual silver in the ma~imum color density area of the film samples which were subjected to ;he wedge-exposure, followed by the processings of Processes 1 and ~, was measured by X-ray fluor~scence analysis. Photographic properties of the films thus processed were compared wi h those of the control sample. The differences in gradation and relative sensitivity ~etween the samples and the control are as shown in Table 4.
~0 Table 4 shows that in the process of ~his inven~ion, a good de-silvering effect and good quality photographic reproduction were obtained and maintained for a long time even when the process was crried out using an automatic developing . processor, whereas in the comparative process in which the time for bleaching was 5 minutes, de-silvering effect and photographic reproduction became worse with time and no de-silvering was effected on the 10th day. Namely, the process of this invention provides stable de-silvering effect and good .

, - ' : , ~. .

quality photographic reproduction which are superior to those provided by the comparative process in which the working time for bleaching was the same (5 minutes) as in the process of this inventionO

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'' ' , 6~ i Example 3 The color negative film No. 10 as described in Table 1 was exposed through a wedge in a similar manner to that of Example 1, followed by color development at 38~C according to the following steps.

Process 1 (Comparative) Color development 3 min. 15 sec.
Bleaching The time as de~cribed in Table 5 Fixing The time as described in Table 5 Washing 3 min. 15 sec.
Stabilizing 1 min. 5 sec.

Process 2 (This invention) Color development 3 min~ 15 sec.
~leaching The time as described in Table 5 Blixing The time as described in Table 5 Washing 3 min. 15 sec.
` Stabilizing 1 min. 5 sec.
Compositions of the solutions used in the processes described above were the same as those described in Example 1, except that the bleaching solution contained a bleach accelerating agent ~bleach accelerator) as shown in Table 5 in an amount as shown also in Table 5.

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The amount of residual silver in the maximum color density area of each of ~he samples thus processed was measured by X-ray fluorescence analysis.
Table 5 shows that the addition of the bleach accelerating agent to the bleaching solution had an excellent effect on the process of this invention which comprises bleaching and blixing steps but it had only a small effect on the comparative process which comprises bleaching and fixing steps.

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~ 6~ 8 Example 4 The same film samples as those described in Example 1 were prepared in a similar manner to ~hat of Example 1, except that the couplers used in the 3rd and 4~h layers in Example 1 were replaced by the following couplers, respectively.
3rd layer: Low speed red-sensitive emulsion layer Comparative compound ~ of Example 1 ... per 1 mole of silver 0.04 mole Coupler EX~ O~per 1 mole of silver 0.003 mole Coupler EX-2 ~ O per 1 mole of silver 0.0006 mole 4th layer: High speed red-sensitive emulsion layer Comparative compound ~ of Example 1 ... per 1 mole of silver 0.02 mole Coupler EX-l .............. ~........... per 1 mole of silver 0.0016 mole ~ The film samples thus prepared were cut into 35 mm-wide film which was then exposed to tungsten light at 25 cms (the color temperature of which had been adjusted to 4,800K
through a filter) through a wedge, followed by the processing according to FUJI COLOR PROCESS CN-16 of FUJI PHOTO FILM CO., LTD. (color development 3 min. 15 sec., bleaching 6 min. 30 sec, washing 2 min. 10 sec., fixing 4 min. 20 sec., washing 3 min. 15 sec., stabilizing 1 min~ 5 sec., followed by drying;
the processing temperature was 38C~ using an automatic ~ 2 ~

developing processor to prepare a control sample. separatelyt the same film samples were exposed through a wedge, followed by the three different processings as described in Table 6 using the automatic developing processor at 38C.

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Compositions of the solutions used in the processes described above were as follows:
Color developing solution (Processes ll to 13) Sodium nitrilo~riace~ate l.9 9 Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1~4 9 Potassium iodide 1.3 mg Hydroxylamine sulfate .2.4 g 4-(N-ethyl-N-~-hydroxyethylamino)-2-methylaniline sulfate 4.5 9 Water to l.0 ~
p~l 10.0 Bleaching solution ~Processes 11 and 13) Ethylenediaminetetraacetic acid, ferric 100.0 g ammonium-salt Ethylenediaminetetraacetic acldf disodium salt 8.0 g Ammonium bromide 150.0 9 Ammonia water ~2~%) 7.0 mQ
Water to 1.0 R
pH 6.0 g7 .
' .

, Fixing solution ~Process 11) Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Aqueous ammonium thiosulfate solution (70%)175.0 m~
S Sodium bisulfite 4.6 g Water to 1.0 p~ 6.6 Blixing solution (Processes 12 and 13) Ethylenediaminetetraacetic acid, ferric ammonium salt 100.0 9 Ethylenediaminetetraacetic acid, disodium salt 4.0 9 Aqueous ammonium thiosulfate solution (70%)17500 m Sodium sulfite 4.5 9 Ammonia water (28~) 15 m Water to l.OR
pH 6.8 Stabilizing solution (Processes 11 to 13) Formalin (40%) 8.0 m~
(Polyoxyethylene para- 5.0 m~
monononylphenyl ether, 0.3 g/~
water to 1.0 Gradation and relative sensitivity of each of the samples thus processed and the control were measured. An ` - 98 -z~

amount of residual silver in the maximum color density area was measured by X-ray fluorescence analysis.
In Process 13, the upper part of ~he bleaching bath of the automatic developing processor was connected to the lower part of the blixing bath by a tube so that the overflow solution from the bleaching bath was introduced into the blixing bath when the replenisher is added to the bleaching bath. For ten sucGessive days, the 35 mm-wide film (100 m per day) was used for outdoor photography, and were then subjected to the processing according to Process 13 while replenishing the following processing solutions. At the same time, the samples exposed through a wedge were also processed every day.

<Amount of each of the solutions replenished per 1 meter ~f tbe 35 mm-wide film ~
Replenisher to the color developing bath 40 m 2 Replenisher to the bleaching bath 20 m~

Replenisher (containing the fixing agent) to the blixing bath 20 m~
Replenisher to the stabilizing bath 40 m~

<Compositions o the replenishers ~
Replenisher to the color developing bath Sodium nitrilotriacetate 1.1 g Sodium sulfite 4.~ g Sodium carbonate 32.0 g Potas~ium bromide 0.7 g Hydroxylamine sulfate 2.6 g _ 99 _ .

' ~8~

4-(N-ethyl-N-~-hydroxye~hylamino)-2-methylaniiine-sulfate 5 0 g Water to 1.0 ~
pH 10.2 Replenisher to the bleaching bath Ammonium bromide 175.0 g Ammonia water ~28%) 4.0 m~
Ethylenediaminetetraacetic acid, erric ammonium salt 110.0 9 Ethylenediaminetetraacetic acid, disodium salt 10 9 Water to 1.0 . pH S.7 Replenisher (containing the ~ixing agent) to the blixing bath Aqueous ammonium thiosulfate solution (70%)400 m~
Sodium sulfite 9 9 Ammonia water ~28%) 12 m~
Sodium bisulfite 10~2 9 Sodium tetrapolyphosphate 4.4 9 Water to 1.0 pH 8.1 8~6~:~

Replenisher to the s~abilizing bath Formalin (40~) 9 m 2 (Polyoxyethylene para- 7 m~
monononylphenyl ether, 0.3 g/
water to 1.0~' Results of the processings are as shown in Table 7.

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The difference in relative sensitivity and the difference in gradation as shown in Table 7 are differences between the control sample and the examples, respectively.
Table 7 shows that the process of this invention provides good quality photographic reproductions and good de-silvering in a shortened ~ime, which are comparable to those obtain~d by the control process and that these effects of the process of this invention are long-lasting.

Example 5 The procedure of Example 4 was repeated to prepare a 35 mm - wi~e film, except that Comparative compound A of Example 1 used in Example 4 was replaced by the coupler o~ ~;e following formula:

OH

C~3 (tlCsH~ Cl~

(~C 5Hl I

.

6~3 The color negative pho~ographic element thus prepared was subjected to the same exposure through a wedge as described in Example 4, followed by the processing according to the Process CN-16 as described in Example 4 using the automatic developing processor.
Separately, the films exposed through a wedge were processed by Processes 14 and 15 as described in Table 8.

Tabl~ 8 , . _ , _ Process 14 (Comparative) Process 15 (This invention) -- _ r , Color development Color development 3 min. 15 secu 3 min. 15 sec.

Bleaching 40 sec.Bleaching 40 sec.

Fixing 3 min. 15 sec. Blixing 3 min. 15 sec.

Washing 3 min. 15 sec. Washing 3 min. 15 sec.

Stabilizing 20 sec. ~ =

Various bleach accelerating agents were used in the processes as described in Table 8.

The processing solutions used in the processes of Table 8 were the same as those used in Processes 11 and 13 of Example 4, except for the following solutions.

-- 10~ --Bleaching solution Ethylenediaminetetraacetic acid, ferric ammonium salt lO0.0 g Ethylenedieminetetraacetic acid, disodium salt 8.0 g Ammonium bromide 80.0 g Ammonia water (28%) 7.0 m Bleach accelerating agent (as described in Table 9) Water to l.0 ~
pH 6.0 Blixing solution lS The same as the bleaching solution described above except that any bleach accelerating agents were not contained 500 m Aqueous ammonium thiosulfate solution (70%) 175 m~
Sodium sulfite 4.0 g 20. Sodium bisulfite 4.6 g Ammonia water (28%) 6.0 m Sodium tetrapolyphosphate 2.0 g For ten successive days, the 35 mm - wide films of the Example (lO0 m per day) were used for outdoor photography, and were then subjected to the processing according to Process 15, while replenishing the following processing solutions. At the same time, the samples exposed through a wedge were also processed e~ery day.

82t~2~
The solution which overflowed from the bleaching bath when the replenisher was added thereto was introduced into the blixing bath in a manner similar to that of Example 4.

~Amount of each of ~he replenishers>
The same as in Example 4O

~Compositions of the replenlshers>
The same as those used in Process 13 of Example 4, except for the following solutionsO

Replenisher to the bleaching bath Ethylenediaminetetraacetic aoid, ~erric ammonium salt 110 g Ammonium bromide 90 g Ammonia water ~28~) . 4 m~
Ethylenediaminete~raacetic acid, disodium salt - 10 g 20 ~ Bleach accelerating agent As described in Table 9 Water to 1.0 ~
pH 5.7 The results of the processings are as shown in Table 9. Table 9 shows that the process of this invention provides good quality photographic reproduction and promotes the effect of the bleach accelerating agent to enable rapid de-silvering.

.~ , . . . ..

, ~'~8~6Z8 Further, it shows tha~ these excellent effects are long-lesting by the introduction of the overflow solution out of the bleaching bath to the blixing bath.

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Example 6 The photographic elements prepared according to Example S were subj~cted to the exposure ~hrough a wedge in a similar manner to that of Example 4, followed by the Process CN-16 using the automa~ic developing procéssor to prepare a control sample.
For ten successive days, the photographic element (100 m per day) were used for outdoor photography, ~ollow~d ~y the processing according to Process 15 as described in Table 8 of Example 5, while replenishing the following processing solutions. A~ the same time, ~he samples exposed through a wedge were also processed every day. Pipework was set up 50 that the solution which overflowed out of the bleaching b~
was introduced into the blixing bath.

<Compositions of the processing solutions>
Color developing solution and Replenisher The same as described in Example 4.

Bleaching solution and Replenisher Diethylenetriaminepentaacetic acid 174 g Ferric chloride hexa hydrate 108 9 Ammonium ~romide 90 g Ammonia water (37%) 190 m Ammonium nitrate ~S g Bleach accelerating agent (Compound IV-1) 2 9 Water ~o 1~0 Q

pH 5.8 :

:. :

z~
Blixing solution The bleaching solution described above 500 m Sodium sulfate 10 g Aqueous ammonium thiosulfate solution (70~)200 m æ
Water to 1.0 pH 7.3 Replenisher to the blixing bath The same as described in Example 4.

Stabilizing solution and Replenisher rhe same as described in Example 4.

Amounts of replenishers added The same as described in Example 4.
The results are as shown in Table lO, which shows ~hat the process of this invention provides good quality pohotographic reproduction and enables good de-silvering.
Table 10 also shows that these effects of this invention are comparable to. those of the control sample and are long-lasting~ .

Table 10 . .
Difference in Difference in relative gradation Residual . Days of sensitivity silver processing _ ~ (~g/cm2) . B G R G R
0 (start) ~0.02 +0.01 -0.01 +0.02 ~0 ~0 1.6 10 days +0.01 + L + + . 02 +o . ol +o . ol 1. 4 Differences in relative sensitivity and in gradation are between the sample of this invention and the control sample, respectivelyO

Claims (14)

1. A method for the processing of a silver halide color photographic element comprising imagewise exposing the element, color developing the exposed element, followed by de-silvering, characterized in that the de-silvering step comprises processing the developed element in a bleaching bath containing a bleaching agent comprising an aminopolycarboxylic acid ferric ion complex salt and subsequently in a blixing bath containing a bleaching agent comprising an aminopolycarboxylic acid ferric ion complex salt and a fixing agent.

2. The method of claim 1, wherein the sllver halide color photographic element contains at least one cyan dye-forming coupler represented by the formula (I) or (II):

wherein R1, R2 and R4 represent a substituted or unsubstituted aliphatic, aryl or heterocyclic group, R3 and R6 represent hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic, aryl or acylamino group, or R3 and R2 represent together a non-metallic atom group which forms a nitrogen-containing five or six member ring, R5 represents a substituted or unsubstituted alkyl group, Z1 and Z2 represent hydrogen or a group which can be released at the time of an oxidative coupling reaction with a developing agent, and n represents 0 or 1.

3. The method of claim 1, wherein the bleaching bath contains at least one bleach accelerator selected from the group consisting of compounds having a mercapto group or a disulfide linkage, isothiourea derivatives and thiazolidine derivatives.

4. The method of claim 1, wherein solution overflowed from the bleaching bath is introduced into the blixing bath.

5. The method of claim 1, wherein the bleaching agent is contained in the bleaching bath in the concentration of 0.1 to 1.0 mole/l.

6. The method of claim 1, wherein the bleaching agent is contained in the blixing bath in the concentration of 0.05 to 0.5 mole/l.

7. The method of claim 1, wherein the blixing agent is contained in the blixing bath in the concentration of 0.3 to 3 mole/l.

8. The method of claim 1, wherein the time for bleaching is 20 seconds to 4 minutes and the time for blixing is 1 to 5 minutes.

9. The method of claim 2, wherein the cyan dye-forming coupler is incorporated in the element in the amount of 2 x 10-3 to 5 x 10-1 mole per mole of silver.

10. The method of claim 3, wherein the bleach accelerator is selected from the compounds represented by the formula (III), (IV), (V), (VI), (VII), (VIII) or (IX):

(III) wherein R1 and R2 may be the same or different and represent hydrogen atom, substituted or unsubstituted lower alkyl or acyl or R1 and R2 may form a ring together and n is 1, 2 or 3, wherein R3 and R4 represent substituted or unsubstituted aliphatic, aryl or heterocyclic group, or R3 and R4 may form a ring together and n is 1, 2 or 3.

(VII) wherein R5 represents hydrogen atom, halogen atom such as chlorine or bromine, amino, substituted or unsubstituted lower alkyl, or alkyl-containing amino group, (VIII) wherein R6 and R7 may be the same or different and each represents hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted phenyl or substituted or unsubstituted heterocyclic, R8 represents hydrogen atom or substituted or unsubstituted lower alkyl and, R9 represents hydrogen atom or a carboxyl group, and (IX) wherein R10, R11 and R12 may be the same or different and each represents hydrogen atom or lower alkyl or, R10 and R11 or R12 may form a ring together, and X represents amino, sulfonic or carboxyl group which may contain one or more substituents.

11. The method of claim 10, wherein the bleach accelerator is contained in the bleaching bath in the concentration of 1 x 10-5 to 1 x 1o-1 mole/l.

12. The method of claim 1, wherein the silver halides incorporated in the color photographic element comprises silver iodide in the amount of 15 mole % or less.

13. The method of claim 1, wherein the color photographic element contains at least 3 9 of silver per square meter of the element.

14. The method of claim 13, wherein the color photographic element contains 3 to 15 g of silver per square meter of the element.