AU611670B2 - Method for processing light-sensitive silver halide color photographic material improved in color restoration badness and processing solution suitable therefor - Google Patents

Description

S F Ref: 52071 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: Related Art: 0 Name and Address of Applicant: Konica Corporation 26-2, Nishi-shinjuku 1-chome Shinjuku-ku Tokyo

JAPAN

Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Address for Service: Complete Specification for the invention entitled: Method for Processing Light-sensitive Silver Halide Color Photographic Material Improved in Color Restoration Badness and Processing Solution Suitable Therefor The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/4 ll s~ L- i ~LYLL IPLII~~ Abstract: Method for processing light-sensitive silver halide color photographic material improved in color restoration badness and processing solution suitable therefor Disclosed is a method for processing a light-sensitive silver halide color photographic material, which comprises subjecting an exposed light-sensitive silver halide color pLotographic material to color developing processing and then applying at least desilverization processing, characterized in that the processing bath to be used in said desilverization processing contains a ferric complex of at least one compound selected from the compounds represented by the formula and the formula (II) shown below, and after said desilverization processing, processing with an alkali bath having a pH of or more and containing a buffering agent is performed, Formula (I) R, -L 1

-^L

3

R:

N-L-N

R, -L2 L -FR Formula (II) L -R6 R, -Ls -N 30 L R 7 wherein L, L to L and R to R 7 are as defined in the specification.

Disclosed in also a processing solution for light-sensitive silver halide color photographic i i_ material, which is an alkali processing solution to be used after an exposed light-sensitive silver halide color photographic material is subjected to color developing processing and desiliverization processing by use of a ferric complex of at least one compound selected from the compounds represented by the formula and the formula (II) shown above.

Method for processing light-sensitive silver halide color photographic material improved in color restoration badness and processing solution suitable thereEor BACKGROUND OF THE INVENTION This invention relates to a Inehtod for processing a light-sensitive silver halide color photographic material and a processing solution to be used for the method, more particularly to a method for light-sensitive silver halide color photographic material which can be applied for a light-sensitive silver halide color photographic material of high sensitivity, high silver content to improve color restoration badness by supressing the leuco formation of cyan dye, and a processing solution to be used for said processing method.

Generally speaking, the basic steps of processing of a color light-sensitive material are color developing step and desilverization step. In color developing step, exposed silver halide is reduced with a color developing agent to generate silver, and the color developing agent oxidized reacts with a color forming agent (coupler) to give a dye image. In the subsequent desilverization, .1 1_i- ~.I_~UII -2 through the action of an oxidizing agent (generally called bleaching agent), the silver generated in the color developing step is oxidized, and thereafter dissolved with a complexing agent of silver ions generally called fixing agent. By passing through the desilverization step, only a dye image can be completed on the color light-sensitive material.

The desilverization step as mentioned above may include the case in which it is carried out in two baths of a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, the case in which it is carried out in a bleach-fixing bath containing the bleaching agent and the fixing agent co-present therein, and further the case in which those baths are combined.

In practical developing processing, in addition to the above basic steps, for maintaining photographic, physical quality of the image, or for improving storability of the image, various auxiliary steps are included. For example, there may be included film hardening bath, stopping bath, image stabilizing bath, water washing bath, etc.

As the bleaching agent in general, red prussiate, bichromate, ferric chloride, ferric complex of aminopolycarboxylic acid, ferric complex of aminopolyphosphonic acid, persulfate, etc. have been known.

However, red prussiate, bichromate involve the problem in environmental pollution concerning cyan compounds, hexavalent chromium, and their uses require special treating installations. Also, in ferric chloride, there are various obstacles in practical application such as the problems of formation of iron hydroxide or generation of stain in the subsequent water washing step. As for 3 persulfate, its bleaching action is very weak, thus involving the drawback of requiring a remarkably long bleaching time. With regard to this point, there is also proposed a method to enhance the bleaching action by using in combination a bleaching accelerator, but persulfate itself is subject to regulation of a dangerous material under Fire Law, whereby various precautions are required in storage. Thus, various drawbacks are involved, which make practical application of persulfate difficult.

In contrast, ferric complex of aminopolycarboxylic acid (typically ferric complex of ethylenediaminetetraaceic acid) has little problem in environmental pollution possesed by the above bleaching agents, and also no problem in storage, and therefore it is the bleaching agent practically applied most broadly at present time.

However, the bleaching power of ferric complex of amnopolycarboxylic acid cannot be necessarily said to be sufficient, and in the processing solution by use of this as the bleaching agent, although the desired object can be accomplished in the case of bleaching or bleach-fixing processing of a low sensitivity light-sensitive silver halide material composed mainly of silver chlorobromide emulsion, in the case of processing of a light-sensitive color photographic material of high sensitivity composed mainly of silver chlorobromoiodide or silver iodobromide emulsion, particularly, a color reversal light-sensitive material for photographing, a color negative lightsensitive material for photographing by use of high silver content emulsion, there have been involved the drawbacks such that desilverization badness occurred, that color restoration badness frequently occurred, and that a long time is required for bleaching.

4i i! 4 For example, in the case of bleaching processing of a color negative light-sensitive material for photographing with the use of a ferric complex of an aminopolycarboxylic acid, at least 4 minutes or longer of bleaching time are required, and also for desilverization subsequent to the bleaching processing, processing with a fixing solution of at least 3 minutes or longer is required. If the bleaching time is attempted to be shortened, there are involved the problems of generation of desilverization badness and color restoration badness as mentioned above, and therefore the bleaching time was elongated. Accordingly, it has been desired to shorten the time required for desilverization time requiring such long time.

As the method for enhancing desilverization performance by shortening the bleaching time, there have been known the method in which pH of the bleaching solution is lowered, the method in which the concentration of the bleaching agent is increased, further the methods in which bleaching accelerators as represented by mercapto compounds as disclosed in U.S. Patent No. 3,893,858, Japanese Unexamined Patent Publications Nos. 95631/1978 and 141623/1978, compounds having disulfide bond as disclosed in Japanese Unexamined Patent Publication No.

95630/1978, thiazolidine derivatives as disclosed in 7 ;Japanese Patent Publication No. 9854/1978, isothiourea derivatives disclosed in Japanese Unexamined Patent Publication No. 94927/1978 are added in the bleaching solution or previous bath. However, the method of lowering pH of the bleaching solution has the drawback that color restoration badness is liable to occur, although bleaching speed may be improved. Also, in the case of increasing the concentration of the bleaching agent, the same drawback as mentioned above is liable to occur, because it cannot be added in large amount due to 1: L 5 the problem of precipitation of iron complex. Also, the method of adding a bleaching accelerator involves the drawback that it is liable to form a difficultly soluble silver complex with silver, and further that it is poorly soluble, and even if used, color restoration is not sufficient.

Accordingly, as described above, it has been required to take a long time for bleaching.

As the method for expediting the desiliverization step, it has been known to perform processing with a bleachfixing solution containing a ferric complex of an aminopolycarboxylic acid and a thiosulfate which is the fixing agent in one bath as disclosed in West German Patent No.

866,605.

However, in the above bleach-fixing solution, because the oxidation power of the ferric complex of aminopolycarboxylic acid is originally weak and moreover the sulfite which is the co-existing preservative and the j thiosulfate which is the fixing agent are reducing agents, they serve to further weaken the oxidation power of the ferric complex of aminopolycarboxylic acid, consequently having the drawbacks of not only lowering desilverization performance, but also readily changing the cyan dye formed in color developing to leuco dye, and also being poor in the ability of developing leuco dye, whereby vital defect of color restoration badness in color reproduction is caused.

The above phenomenon will appear more conspicuously with lapse of time when the light-sensitive material is processed continuously over a long term.

The present inventors have investigated variously on the -L L 6 above problems, and consequently found that the above.

coloration restoration badness is a problem generated commonly when a ferric complex of an aminopolycarboxylic acid and a ferric complex of an aminopolyphosphonic acid are used as the bleaching agent in the bleaching solution or the bleach-fixing solution in the desilverization step, which problem becomes particularly great as the result of the action of the ferric complex of aminopolycarboxylic acid or amnopolyphosphonic acid as the oxidizing agent, whereby ferrous complex (complex ions) of aminopolycarboxylic acid or aminophosphonic acid formed by reduction of itself is accumulated in the processing solution or the light-sensitive material.

Also, accumulation of the above ferrous complex ions depends on pH of the bleaching solution or bleach-fixing solution, and it has been found that formation of ferrous complex ions will occur more readily as the pH is higher.

Further, it has been found that formation of ferrous complex ions, in addition to the phenomenon cdused by decomposition of the ferric complex of aminopolycarboxylic acid or aminopolyphosphonic acid, when using a bleach-,fixing solution, also occurs by reduction of the ferric complex ions with the sulfite contained as the preservative in the bleach-fixing solution, or alternatively the ferric complex itself is reduced by oxidizing silver by processing of a light-sensitive material of high silver content to become ferrous complex ions, whereby ferrous complex ions exist at high concentration in the coating of the light-sensitive photographic material during processing to covert cyan dye to leuco dye.

Color restoration badness due to such leuco formation of cyan dye has been particularly marked in a lightsensitive color photographic material of high i 7 sensitivity, high silver content type with a thickness of 13 pm or more.

When the above ferrous complex ions are accumulated at high concentration in the bleaching solution or the bleach-fixing solution, the ferrors complex ions in the coating of the light-sensitive photographic material formed in the bleaching reaction is remarkably inhibited in diffusion outside of the coating, whereby it may be considered that formation of leuco dye is increased to make greater the color restoration badness.

Generally speaking, for activating the above ferrous complex ions of aminopolycarboylic acid or aminophosphonic acid to ferric complex ions by oxidation, the method called aeration which performs oxidation by blowing air into the processing solution has been well known in the art.

However, this method also oxidizes the sulfite which is a preservative, and therefore, although there is no danger when renewal ratio of the solution is relatively higher with relatively greater amount of processed amount as in the case of processing of color paper, etc., oxidation of the solution will proceed too far in the case of relatively smaller processing amount as in color nega, whereby the sulfite which is a preservative is oxidized and the thiosulfate decomposed to precipitate sulfur (sulfide) to form a precipitate, thus involving a danger of causing a vital inconvenience.

Therefore, it has been strongly demanded to have a method which does not cause color restoration badness even if there may exist ferrous complex ions to some e,:tent.

Also, it has been known that the above coloration badness of 8.0 or more and containing a buffering agent is performed, Formula I /2 8 -8can be improved by enhancing the pH of the bleaching solution or bleach-fixing solution, but as described in U.S. Patent No. 3,773,510, when pH of the bleaching solution or bleach-fixing solution is increased, not only the bleaching power is contrariwise weakened, but also ammoniums of ammonium thiosulfate and ferric ammonium salt will be readily volatilized, whereby the odor generated will cause contamination of the environment.

Thus, it is impossible to realize increase of pH of the bleaching solution or bleach-fixing solution for improvement of color restoration badness.

Also, in U.S. Patent No. 3,189,452, there is disclosed the method in which a red prussiate bleaching solution is used after bleaching, fixing to return the leuco dye to cyan dye by oxidation. However, use of red prussiate involves the problem in environmental pollution as mentioned above, and therefore there is involved the drawback that extremely difficult operation for recovery of red prussiate is accompanied for practical application.

Therefore, it has been strongly demanded to provide a processing method which will not cause color restoration badness even if ferrous complex ions may be accumulated when a long term running is performed.

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a method for processing a light-sensitive silver halide color photographic material by which leuco formation of cyan dye will occur with difficulty even in processing of a light-sensitive color photoraphic material, particularly a light-sensitive silver halide color photographic material having a high film thickness -9of the high sensitivity high silver amount type and a processing solution to be used for said processing method. A second object of the present invention is to provide a method for developing a dye which can be practiced easily without problem in environmental pollution.

According to a first embodiment of this invention, there is provided a nathod for processing a light-sensitive silver halide color photographic material, which comprises subjecting an exposed light-sensitive silver halide color photographic material having silver on a support thereof in an amount of 20 mg or more per 100 cm 2 of the surface area of the support, to color developing processing and then applying at least desilverization processing, characterized in that the processing bath to be used in said desilverization processing contains a ferric complex of at least one compound selected from the compounds represented by the formula and the formula (II) shown below, and after said desilverization processing, processing with an alkali bath having a pH of 8.0 or more and containing a buffering agent is performed, Formula I R L

L

3

R

3 L R L2 L L- R 2 2 4 4 Formula II

L

6

R

6

R

5

L

5

N

R7 wherein L represents an alkylene group, a cycloalkylene group, a phenylene group, -L 8 -0-L 8

-O-L

8 or -L 9

-Z-L

9 where Z 0"Oo, represents N N-R0 or L13-- -L12-R 9

L

1 2

-R

9 R11 R11

L

1 to LI3 each represent an alkylene group; R 1 to RI each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt); with proviso that at least two of R1 and R4 are carboxylic acid /\''groups (including salts thereof) or phosphonic acid groups (including LMhtlO I0 represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt); with proviso that at least two of R 1 and R 4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including hL Ii m n 10 salts thereof), and at least one of R 5 to R7 is a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt).

According to a second embodiment of this invention, there is provided a processing solution for light-sensitive silver halide color photographic material, which is an alkali processing solution to be used after an exposed light-sensitive silver halide color photographic material having silver on a support thereof in an amount of 20 mg or more per 100 cm of the surface area of the support, is subjected to color developing process and desilverization processing by use of a ferric complex of at least one compound selected from the compounds represented by the formula and the formula (II) shown below, said alkali processing solution having a pH of or more and containing a buffering agent, Formula I R L N- L-L

R

R1 LI L- N' L3 R 3 R R 4 R2 4 4 Formula II L6 R6 1 R LR N R5 5 LN-R 7 7 wherein L represents an alkylene group, a cycloalkylene group, a phenylene group, -L8-0-L -0-Lg- or -L9-Z-L9-; where Z represents

N-L

10 -N-L N- N-R 10 or -N-L 3

-N-

-L12-R 9

L

12

-R

9

R

11

R

11

L

1 to L 13 each represent an alkylene group; R to R11 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt); o'o with proviso that at least two of R and R are carboxylic acid o groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R 5 to R 7 is a carboxylic acid group (including its salt) or a p~osphonic acid group (including its Ssalt).

LMM/1300y LH. I 10A As further preferred embodiments, the above objects can be accomplished further efficiently by containing a chelating agent with a chelate stability constant with iron ions (logKMA) of 6 or more in the above alkali bath, containing 1 x 10 3 mol or more of ferric complex of an aminopolycarboxylic acid per 1 liter of the bath in the above alkali bath, containing an oxidizing agent in the above alkali bath.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, after desilverization processing by use of a ferric complex of at least one 4 0 0R 4 C) 4.

LI

4 4 4 LMM/l 300y 5845/4 11compound selected from the compounds represented by the formula and the formula (II) (hereinafter called ferric complex of the compound of the present invention) as the bleaching agent, by processing with an alkali bath with pH of 8.0 or higher, the ferrous complex ions of the compound of the present invention formed and accumulated by adsorption in the gelatin coating of the lightsensitive silver halide color photographic maerial are desorbed, diffused quickly out of the above gelatin coating to make the atmosphere alkaline, whereby developing of cyan dye is remarkably accelerated to improve color restoration badness.

In the present invention, the desilverization processing applied after the color developing step can be any step, provided that the ferric complex of the compound of the preent invention is used as the bleaching agent, but a preferable representative desilverization step by application of the present invention is as exemplified below.

Bleaching fixing Bleach-fixing o°0n Bleaching bleach-fixing Bleaching bleach-fixing fixing Bleach-fixing bleaching fixing Fixing bleaching bleach-fixing In the above desilverization step, in the bleaching and bleach-fixing processing bath, namely the processing solution having bleaching ability, the ferric complex of the compound of the present invention is used as the bleaching agent.

The compound of the present inventon is at least one compound selected from the compounds represented by the Disclosed in also a processing solution for light-sensitive silver halide color photographic o V U-p 12 formula and the formula (II) shown below: Formula (I)

R

2

-L

2

-K

3 N-L-N 4 Formula (II) 0 5

-L

5 S-L R

-N

-R7 wherein L represents an alkylene group, a cycloalkylene group, a phenylene group,

-L

8

-O-L

8

-O-L

8 or -L 9

-Z-L

9 where Z represents N-L0-R8, N- ,-N-R10 or -N-L -N- 108' I 1 10 131

-L

1 2

-R

9 L12-R 9 R11 R11

L

1 to L13 each represent an alkylene group; R 1 to

R

1 1 each represent a hydrogen atom, hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt); with proviso that at least two of R 1 to R 4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R 5 to R 7 is a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt).

The ferric complex of the compound of the present invention to be used in the processing solution having bleaching ability of the present invention is a complex of ferric ions (Fe 3 with a compound of the present invention.

In the following, representative specific examples of the 13 compound of the present invention are shown.

A-i Ethylenediaminetetraacetic acid A-2 Disodium ethyienediaminetetraacetate A-3 Diammonium ethylenediaminetetraacetate A-4 Tetra (trimethylammonium) ethyienediaminetetraacetate Tetrapotassiurn ethyiened iami netetraacetate A- 6 Tetrasodium ethyienediaminetetraacetate A-7 Trisodium ethyienediaminetetraacetate A-8 Ammonium diethyienetriaminepentaacetate A-9 Pentasodium diethyienetriaminepentaacetate Ethyienediamine-N-C -oxyethy1)-N,N' ,N'-triacetic acid A-il Trisodium ethylenediamine-N-( -oxyethyi)-N,N1,N'triacetate A-12 Triammonium ethylenediamine-N-( -oxyethyl)-N,N' triacetate A-13 Ammonium propyienediaminetetraacetate A-14 Diso-lium propyienediaminetetraacetate A-15 Nitriiotriacetic acid A-16 Sodium nitrilotriacetate A-17 Cyclohe :anediaminetetraacetic acid A-18 Di sodium. cyciohexanediaminetetraacetate A-19 Iminodiacetic acid A-20 Dihydroxyethyigiycine A-21 Ethyl ether diaminetetraacetic acid A-22 Glycol ether diaminetetraacetic acid A-23 Ethyienediaminetetrapropionic acid A-24 Ammonium i,2-diaminopropanetetraacetatLe A-25 Sodium i,2-diaminopropanetetraacetate A-26 Ammonium hydroxyiminodiacetate A-27 Sodium hydroxyiminodiacetate A-28 Triethyienetetraminehexaacetic acid A-29 i,3-Diaminopropane-2-oi-tetraacetic acid A-30 Phenyienediaminetetraacetic acid A-31 Nitrilotripropionic acid Y.L V U C U.Y t- LULG t= I II I -14 A-32 Ethylenediaminetetramethylenephosphonic acid A-33 Diethylenetriaminepentamethylenephosphonic acid A-34 Cyclohexanediaminetetramethylenephosphonic acid Nitrilotrimethylenephosphonic acid A-36 Iminodimethylenephosphonic acid Among these compounds, aminopolycarboxylic acids are preferred, particularly preferably A-i to A-3, A-8, A-13, A-14, A-17 to A-19, A-22, A-24 to A-27.

The ferric complex of the compound of the present invention to be used in the present invention may be used in the form of a complex, or a ferric ion complex may be formed in a solution by use of a ferric salt, for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. together with the compound of the present invention. When used in the form of a complex, one kind of complex may be used, or two or more kinds of complexes may be used. On the other hand, when a complex is formed in a solution by use of a ferric salt and the compound of the present invention, one or two or more kinds of the ferric salt may be used. Further, one or two or more kinds of the compound of the present invention may be also used. In either case, the compounds of the present invention may be used in an excess more than forming a ferric ion complex.

Also, in the solution having bleaching ability containing the above ferric ion complex, metal ion complex of metals other than iron such as cobalt, copper, nickel, etc. may be contained.

In the solution having bleaching ability of the present invention, the above ferric complex of the compound of the present invention may be preferably in the range from i. the problems of formation of iron hydroxide or generation of stain in the subsequent water washing step. As for I II I Z 0.05 to 2 mol, more preferably from 0.1 to 1.0 mol, particularly preferably from 0.2 to 0.6 mol, per 1 liter of the solution having bleaching ability.

In the desilverization step of the present invention, when employing a bleaching solution, the bleaching solution can contain, in addition to the ferric complex of the compound of the present invention as the above bleaching agent, any of known additives which can be used in conventional bleaching solution, including buffering agents comprising various salts of boric acid, borax, metaboric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc., halide compounds such t as potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, I potassium iodide, sodium iodide, ammonium iodide, etc.

The pH of the bleaching solution of the present invention may be preferably in the range from 4.0 to 8.0, more S"",preferably from 5.0 to When a bleach-fixing solution is used in the desilverization step of the present invention, in the bleach-fixing solution, in addition to the compounds which can be added in the above bleaching solution, there may be employed a compound capable of forming a watersoluble complex through the reaction with a silver halide as used in conventional fixing processing as the silver halide fixing agent, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate and thiocyanate such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thiourea, thioether, highly concentrated bromide, iodide, etc. These fixing agents can be used in amounts within 1.K LI-uL a long time is required for bleaching.

16 16 the range which can be solved of 5 g/liter or more, preferably 50 g/liter or more, more preferably 70 g/liter or more.

Further, various optical brighteners, defoaming agents, surfactants or antifungal agents can be also contained.

It is also possible to incorporate appropriately preservatives such as hydroxylamine, hydrazine, sulfite, metabisulfite, bisulfite adduct of aldehyde or ketone compound, etc.; organic chelating agents such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, etc. or stabilizers such as nitro alcohol, nitrate, etc.; solubilizing agents such as alkanolamine, etc.; stain preventives such as organic amine, etc.; other additives; or organic solvei.:s such as methanol, dimethylformamide, dimethyl sulfoxide, etc.

The pH of the bleach-fixing solution of the present invention may be preferably in the range from 3.0 to 9.8, more preferably from 5.6 to 8.5, particularly preferably from 6.0 to 8.3.

When a fixing solution is used in the desilverization step of the present invention, the fixing solution contains a fixing agent such as thiosulfate, thiocyanate, etc. as mentioned above for bleach-fixing solution as the silver halide fixing agent.

Also, as the preservative for the fixing agent, preservatives such as hydroxylamine, hydrazine, sulfite, metalbisulfite, bisulfite adducts of aldehyde or ketone compounds, etc., further known additives conventionally used in fixing solution such as various pH buffering agents as mentioned for bleaching solution, halide Jb agent, the same drawback as mentioned above is liable to Occur, because it cannot be added in large amount due to i 17compounds, etc. can be contained.

The pH of the fixing solution may be preferably in the range from 5.0 to 8.5, more preferably from 6.0 to In the above desilverization processing step, a part or all of the bleaching bath overflow solution used which flow out from the bleaching bath as the result of addition of bleaching replenishing solution into the bleaching bath, and a part or all of the fixing bath overflow solution used which flow out from the fixing bath as the result of addition of fixing replenishing solution into the fixing bath, respectively can be introduced into the bleach-fixing bath. In that case, overflow solutions from the both bleaching and fixing baths can be reutilized effectively, without giving bad influence on desilverization peformance, and also reduction in the total amount of replenishing solution is possible. Thus, it is a preferred embodiment.

In the present invention, the light-sensitive silver halide color photographic material subjected to the above desilverization processing is processed in an alkali bath having pH of 8.0 or higher and containing a buffering agent. Here, during processing in an alkali bath, processing in an alkali bath may be practiced continuously after the desilverization processing, as a matter of course, and also before the alkali bath processing, water washing, rinsing, and further the water washing substitutive stabilization which extremely reduces the amount of washing water, etc. may be applied.

In view of the cost, etc., it is preferable to perform the alkali bath processing continuously after the desilverization processing.

The above alkali bath can be operated by maintaining its 18 pH value at 8.0 or more, specifically pH 8.0 to 14.0, preferably 8.0 to 12.0, more preferably 8.5 to 12.0, most preferably 9.0 to 11.5 In the following, the alkali processing solution having pH of 8.0 or higher and containing a buffering agent of the present invention (hereinafter called merely alkali bath of the present invention) is to be described.

As the buffering agent to be used in the alkali bath of the present invention, any compound having stable buffering action in an aqueous solution of pH 8.0 or higher may be employed. Specific examples may include inorganic salts such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, boric acid, borax, sodium metaborate, sodium phosphate, potassium phosphate, sodium primary phosphate, etc.; amines such as ethanolamine, ethylenediamine, methylamine, trimethylamine, propylamine, etc.; amino acids such as hydroxyproline, leucine, glycine, alanine, aspartic acid, y-aminobutylacetic acid, etc.; various organic compounds such as sulfosalicylic acid, piperazine, guanidine, etc., and these can be used either alone or in combination.

As the buffering agent to be used in the present invention, in view of the cost, the color restoration badness improvement effect of the present invention, the pH maintenance effect during continuous use over a long term and further bad influence on other photographic performances, sodium carbonate, potassium carbonate, potassium bicarbonate, boric acid, borax, sodium metaborate, sodium phosphate, potassium phosphate, sodium primary phosphate, sulfosalicylic acid, etc. may be preferably used. Although the buffering agetn may serve as an alkali agent, an alkali agent such as sodium ii cyan dye has been particularly marked in a lightsensitive color photographic material of high 19 hydroxide and potassium hydroxide may be added separately.

The amount of the above buffering agent used in the alkali bath of the present invention may differ greatly depending on the pH of the alkali bath, the kind of the buffering agent employed, and if it is used in too much amount, staining may be generated on the processed light-sensitive material, or if it is too small, the problem such as small buffering effect, etc. may ensue.

Thus, although it may be determined depending on the alkali bath conditions, as a measure, an amount ranging from 0.2 to 50 g per one liter of the alkali bath, more a preferably 0.5 to 30 g may be employed.

o The alkali bath processing in the present invention can be done without problem by use of one or multiple tanks, but preferably 1 to 2 tanks may be employed.

Also, the alkali bath of the present invention may be used similarly as the manner in which other processing baths for photography are used, specifically with sufficient supply of a replenishing solution, but it is preferable to make the amount replenished minimum in view of environmental pollution, etc.

o The amount of the processing solution carried over from the preceding bath into the alkali bath may differ depending on the kind of the light-sensitive material, the conveying speed and conveying sysem of the automatic developing machine, the squeezing system of the lightsensitive material surface, etc., but in the present invention, the amount carried over may be preferably ml/m 2 to 150 ml/m 2 with the unit area of the lightsensitive material processed as the standard, and the replenished amount at which the effect of the present i' Also, it has been known that the above coloration badness 20 invention is more marked for the amount carried over may 2 2 be in the range from 50 ml/m to 3.0 liter/m with the replenished amount with particularly remarkable effect being in the range from 100 ml/m 2 to 950 ml/m 2 In the above alkali bath of the present invention, a chelating agent with a chelate stability constant with iron ions (logKMA) of 6 or more can be incorporated, whereby the effect of the present invention, specifically improvement of the color restoration badness can be effectively accomplished. Also, it has the effect of preventing effectively formation of hydroxides of soluble irons salts carried over into the alkali bath.

Here, the chelate stability constant means the constant generally known by L.G. Sill, en. A.E. Martell, "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964), S. Chaberek, A.E.

Martell, "Organic Sequestering Agents", Wiley (1959), etc.

In the present invention, chelating agents with chelate stability constant for iron ions of 6 or more, there may be included organic carboxylic acid chelating agents, organic aminopolycarboxylic acids, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. The above iron ions mean both of ferric ions (Fe and ferrous 2+ ions (Fe In the present invention, specific compound examples having chelate stability constant with iron ions of 6 or more may include the following compounds, which are not limitative of the present invention. That is, there are ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, i_ i color photographic material having a high film thickness 21 hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethlenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanolteraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacctic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene- 1,1-diphosphonic acid, 1,l-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-l,2,4-tricarboxylic acid, l-hydroxy-l-phosphonopropane-l,2,3-tricarboxylic acid, acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, of which particularly preferred are diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, ethylenediaminetetraacetic acid and salts thereof.

The amount of the above chelating agent used in the present invention may be in the range from 0.01 to 50 g, preferably from 0.05 to 20 g, to give good results.

In the present invention, it is extremely preferable in improving the color restoration badness to incorporate a complex of the above chelating agent with iron ions, namely iron complex, in the alkali bath. Particularly preferable compounds may include ferric sodium ethylenediaminetetraacetate, ferric sodium diethylenetriaminepentaacetate, ferric sodium propylenediaminatetraacetate, ferric sodium 1,2-diaminopropanetetraacetate, etc., and it may be added in an amount of 0.5 to 30 g, particularly preferably 2 to 15 g, per liter of the alkali oath.

In the present invention, by permitting the overflow .t with proviso that at least two of R and R are carboxylic acid S. groups (including salts thereof) or phosphonic acid groups (including LM *'0 i 22 solution of the above solution having bleaching ability to flow into the alkali solution and have the ferric complex of an aminopolycarboxylic acid exist at a concentration of 1 x 10 3 mol or higher per one liter of the alkali bath, further color restoration badness can be well prevented.

Also, by incorporating an oxidizing agent in the alkali bath, for example, hydrogen peroxide, sodium percarbonate, sodium p-rborate, potassium persulfate, ammonium persulfate, sodium perchlorate, sodium hypochlorite, potassium hydrobromide, ammonium hydrobromide, sodium hydrobromide, etc., further color restoration badness can be well prevented. The amount of the oxidizing agent may be preferably 0.01 g to g/liter.

In the processing method of the present invention, the above alkali bath processing may be the final step, or further water washing processing or processing with stabilizing processing substantially without use of washing water may be practiced.

In the present invention, as the processing after the alkali bath, stabilizing processing substantially without use of washing water of the latter is preferred.

The components in the stabilizing solution may comprise basically only water, but various compounds can be also added, and the compounds preferably used in the present invention may include formalin, surfactants, ammonium salts, chelating agent and metal salts.

In the above alkali bath or stabilizing solution of the present invention, an antifungal agent may be used, if necessary. Useful antifungal agents may include I t.

A-

group (including its salt) or a phosphonic acid group (including its salt).

LMM7i300y -23hydroxybenzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, quaternary ammonium compounds, urea compounds, isooxazole compounds, propanolamine compounds, sulfamide derivatives, amino acid compounds, triazine compounds and benzotriazole compounds.

In the processing method of the present invention, in addition to the steps of color developing, desilverization processing and the alkali bath processing according to the present invention, there may be also added various auxiliary steps such as film hardening, neutralization, monochromatic developing, reversal, the step of washing with small amount of water, etc., if necessary.

The light-sensitive silver halide color photographic material to be applied for the processing method of the S 20 present invention is not basically limited in its kind, but particularly effectively used in the present Sinvention are high sensitivity photographic lightsensitive materials having silver halide grains containing 0.5 mol% or more, preferably 3 to 10 mol% of silver iodide in at least one layer of the silver halide emulsion layers. Also, it is a light-sensitive material o in which the sum of the dried film thicknesses of the all photographic constituent layers on the side having the silver halide emulsion layer on the support should be S 30 preferably 13 pm or more preferably 15 um to 28 pm, more preferably 17 pm to 24 pm, and further a high silver content light-sensitive material in which the amount of the coated silver on the support may be 20 mg/100 cm 2 or more, preferably 30 mg/100 cm 2 to 80 mg/100 cm 2 more preferably 40 mg/1 0 0 cm 2 to 70 mg/100 cm i jL r LMM/1300y 24 The silver halide emulsion of the light-sensitive silver halide color photographic material applicable for the present invention can be chemically sensitized in conventional manner, and optically sensitized to a desired wavelength region by use of a sensitizing dye.

In the silver halide emulsion, antifoggant, stabilizer, etc. can be added. As the binder for said emulsion, gelatin may be advantageously used.

The emulsion or other hydrophilic colloid layers can be subjected to film hardening, and also plasticizers, dispersions of water-insoluble or difficultly soluble synsthetic polymers (latex) can be incorporated therein.

In the emulson layer of the light-sensitive material for color photography, a coupler is used.

Further, there can be used colored couplers having the effect of color correction, competitive couplers, and compounds releasing useful fragments for photography such as developing accelerator, bleaching accelerator, developer, silver halide solvent, color controller, film hardening agent, foggant, antifoggant, chemical sensitizer, spectral sensitizer and desensitizer through coupling with the oxidized product of a developing agent.

In the light-sensitive material, auxliary layers such as filter layer, halation preventive layer, irradiation 30 preventive layer, etc. can be provided. In these layers and/or the emulsion layers, a dye flowed out from the light-sensitive material or bleached during developing processing may be also contained.

In the light-sensitive material, matting agent, lubricant, image stabilizer, surfactant, color H 4 compound selected from the compounds represented by the antifoggant, developing accelerator, developing retarder or bleaching accelertor can be added.

As the support, papers lamianted with polyethylene, etc., polyethyleneterephthalate film, baryta paper, cellulose triacetate, etc. can be used.

The present invention is described in detail by referring to the following Examples, by which the embodiments of the present invention are not limited at all.

Example 1 Simulating the layer constitution employed for high sensitivity light-sensitive silver halide color photographic material in this field of art, while interposing various auxiliary layers, black colloidal silver halation preventive layer, red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer were arranged from the support side, and a mono-dispersed high sensitivity silver halide emulsion layer was arranged at the outermost side of said bluesensitive silver halide emulsion layer. The amount of silver coated was 60 mg/100 cm and the dried film thickness was made 25 pm.

Layer g of black colloidal silver obtained by reducing silver nitrate with the use of hydroquinone as the reducing agent exhibiting high absorption at a wavelength of 400 to 700 nm was dispersed in 3 g of gelatin to prepare a dispersion and a halation preventive layer was provided by coating.

Layer intermediate layer comprising gelatin.

In the following, representative specific examples of the ;i;i 26 Layer 3...low sensitivity red-sensitive silver halide emulsion layer containing 1.5 g of a low sensitivity red-sensitive silver iodobromide emulsion (AgI; 7 mol%), 1.6 g of gelatin and 0.4 g of tricresyl phosphate hereinafter called TCP) containing 0.80 g of l-hydroxy-4-( B-methoxyethylaminocarbonylmethoxy)-N-[6- 2,4-di-t-amylphenoxy)butyl]-2-naphthoamide (hereinafter called cyan coupler and 0.028 g of l-hydroxy-4-[4-(l-hydroxy-8acetamido-3,6-disulfo-2-naphthyl-azo)phenoxy]- N-[6-(2,4-di-amylphenoxy)butyl]-2-naphthoamide* disodium (hereinafter called colored cyan coupler dissolved therein.

Layer 4.. high sensitivity red-sensitive silver halide emulsion layer containing 1.1 g of a high sensitivity red-sensitive silver iodobromide emulsion (AgI; 6 mol%), 1.2 g of gelatin and 0.15 g of TCP containing 0.23 g of cyan coupler and 0.020 g of colored cyan coupler (CC-1) dissolved therein.

Layer 5...intermediate layer containing 0.04 g of dibutyl phthalate (hereinafter called DBP) containing 0.07 g of (hereinafter called staining preventive (HQ-1) and 1.2 g of gelatin.

Layer 6...low sensitivity green-sensitive silver halide emulsion layer containing 1.6 g of a low sensitivity green-sensitive silver iodobromide emulsion (AgI; 12 mol%), 1.7 g of gelatin and 0.3 g of TCP containing three kinds of couplers of 0.30 g of l-(2,4,6-trichlorophenyl)-3-[3-(2, i A-31 Nitrilotripropionic acid 1 i, -27pyrazolone (hereinafter called magenta coupler 0.20 g of 4,4-methylenebis-ll-(2,4,6trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxy- (hereinafter called magenta coupler and 0.066 g of l-(2,4,6-trichlorophenyl)-4-(l-naphthylazo)- 3-(2-chloro-5-octadecenylsuccinimidoanilino)-5pyrazolone (hereinafter called colored magenta coupler dissolved therein.

Layer 7...high sensitivity green-sensitive silver halide emulsion layer containing 1.5 g of a high sensitivity green-sensitive silver iodobromide emulsion (Agl; 10 mol%), 1.9 g of gelatin and 0.12 g of TCP containing 0.093 g of magenta couplet 0.094 g of magenta coupler (M-2) and 0.049 g of colored magenta coupler (CM-1) dissolved therein.

Layer 8...yellow filter layer containing 0.2 g of yellow colloidal silver, 0.11 g of DBP containing 0.2 Sg of stain preventive (HQ-1) dissolved therein and 2.1 g of gelatin.

Layer 9...low sensitivity blue-sensitive silver halide emulsion containing 0.95 g of a low sensitivity blue-sensitive silver iodobromide emulsion (AgI; 7 mol%), 1.9 g of gelatin and 0.93 g of DBP containing 1.84 g of a-[4-(l-benzyl-2- S 30 phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-apivaloyl-2-chloro-5-[y-(2,4-di-t-amylphenoxy)butaneamidolacetanilide (hereinafter called yellow coupler dissolved therein.

Layer 10..high sensitivity blue-sensitive silver halide emulsion layer containing 1.2 g of a high the present invention may be preferably in the range from 28 i sensitivity mono-dispersed blue-sensitive silver iodobromide emulsion (AgI; 6 mol%), g of gelatin and 0.23 g of DBP containing 0.46 g of yellow coupler dissolved therein.

Layer 11..the second protective layer comprising gelatin.

Layer 12..the first protective layer containing 2.3 g of gelatin.

This sample was cut into pieces, and by use of the piece to which wedge exposure was given in a conventional manner, processing was performed by use of a processing device for piece according to the following steps (hereinafter called hand developing processing).

Processing step Processing Number of Processing time temp. tanks i. Color 37.8 1 3 min. 15 sec.

developing 2. Bleach-fixing 37.8 1 3 min. 30 sec.

(pH of bleach-fixing solution was made as shown below in Table 1) 3. Alkali bath 30 34 2 3 min. 30 sec.

(pH of alkali bath was made as shown below in Table 1) 4. Stabilizing 30 34 1 2 min. 10 sec.

Drying For the color developing solution, the bleach-fixing solution, the alkali bath solution and the stabilizing solution, those shown below were used.

[Color developing solution) Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 5.0 g etc. These fixing agents can be used in amounts within 29 Sodium bromide 1.2 g Potassium iodide 2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g Sodium diethylenetriaminepentaacetate 2.0 g N-ethyl-N-p-hydroxyethyl-3-methyl-4aminoaniline sulfate 4.5 g Potassium hydroxide 1.2 g (made up to one liter with addition of water, and adjusted to pH 10.06 with sodium hydroxide or 20% sulfuic acid) [Bleach-fixing solution] Ammonium !thylenediaminetetraacetate 2.0 g Ferric diammonium ethvlenediaminetetraacetate (complex of exemplary compound No. A-3) 150 g Aqueous ammonium thiosulfate 250 ml Ammonium sulfite 10 g Mercaptobenztriazole 2.5 g Ammonia water 7.3 ml (made up to one liter with addition of water, and adjusted to pH as shown in Table 1 with acetic acid and S, ammonia water) Further, with addition of silver powder, ferric diammonium ethylenediaminetetraacetate was reduced so as to form 40 g of ferrous diammonium ethyelenediaminetetraacetate, and again pH was adjusted S 30 as shown in Table 1.

[Alkali bath solution] Diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate 10 g Borax 2.0 g (made up to one liter with addition of water, and pH was used in fixing solution sucn as VdULUJ-u agents as mentioned for bleaching solution, halide 30 adjusted as shown in Table 1 with potassium hydroxide or sulfuric acid) [Stabilizing solution] Formalin (37% aqueous solution) Sodium diethylenetriaminepentaacetate Konidax (produced by Konishiroku Photo Industry K.K.) 2 ml 2 g 5 ml Ammonium sulfate 1 g (made up to one liter with addition of water, and pH adjusted to 3.0 with sulfuric acid) C 0 0) 0) 0) 1 The above alkali bath can be operated by maintaining its i- -e 31 Table 1 Experimental No. Bleach-fixing Alkali bath pH solution pH 1-1 1-2 1-3 1-4 1-6 1-7 1-8 1-9 1-10 1-11 1-12 1-13 1-14 1-15 1-16 1-17 1-18 1-19 1-20 1-21 1-22 1-23 1-24 1-25 1-26 1-27 1-28 1-29 1-30 1-31 1-32 1-33 (Comparative) (This inv.

Comparative) (This inv.

"Ce)

)I

(Comparative) (This inv.

)I

(Comparative) (This inv. (Comparative) (This inv. 4.0 11

II

It

II

It

II

It 5.0 10.0 11.0 12.0 13.0 14.0 10.0 11.0 12.0 13.0 14.0 10.0 11.0 12.0 13.0 14.0 10.0 11.0 6.0

II

II

II

I"

7.0

II

II

II

II

as an alkali agent, an alkali agent such as sodium p; 32 Table 1 (cont'd) Experimental No.

1-34 (This inv.

1-35 1-36 1-37 (Comparative) 1-38 1-39 (This inv.

1-40 1-41 1-42 1-43 1-44 1-45 1-46 (Comparative) 1-47 1-48 (This inv.

1-49 1-50 1-51 1-52 1-53 1-54 1-55 (Comparative) 1-56 1-57 (This inv.

1-58 1-59 1-60 1-61 1-62 1-63 Bleach-fixing solution pH Alkali bath pH 7.0 12.0 13.0 I" 14.0 8.0 10.0 11.0 12.0 13.0 14.0 9.0 10.0 11.0 12.0 S13.0 14.0 10.0 I" 10.0 11.0 12.0 13.0 I" 14.0 sensitive material processed as the standard, and the replenished amount at which the effect of the present 33 Following the above recipes, light-sensitie material samples were processed, and the residual silver amount (mg/dm 2 at the maximum density portion in the sample after processing was measured by fluorescent X-ray method. Further, after the cyan dye density was measured by use of Sakura photoelectric densitometer (produced by Konishiroku Photo Industry and by use of this value, with the cyan dye density after processing of the same sample with a 3% red prussiate solution in a conventional manner at room temperature for 3 minutes as being 100, the color restoration ratio was calculated.

The results are summrized in Table 2.

ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, 34 Table 2 Experimental No. Residual silver amount (mg/din 2 nione Color restoration ratio 1-1 (Comparative) 1-2 1 1-3 (This inv.

1-4 C 1 C t 1-6 it 1-7 1-8 C 1-9 1-10 (Comparative) 1-11 C o 1-12 (This inv.

1-13C 1-14C 1-15C 1-16C 1-17C 1-18( 1-19 (Comparative) 1-20 C 1 1-21 (This inv.

1-22 C t 1-23 It 1-24( 1-25C 1-26C 1-27( 1-28 (Comparative) 1-29 C 1 1-30 (This inv.

1-31 1 1-32 C t 1-33 It II 89 II 97 II 100 I 100 II 22 II 26 64 II 96 II 100 It 100 II 36 11 100 In the present invention, by permitting the overflow

"I

35 Table 2 (cont'd) Experimental No.

2-34 1- 5 1-36 1-37 (Comparative) 1-38 1-39 (This inv. 1-40 1-41 1-42 1-43 1-44 1-45 1-46 (Comparative) 1-47 1-48 (This inv.

1-49 1-50 1-51 1-52 1-53 1-54 1-55 (Comparative) 1-56 1-57 (This inv.

1-58 1-59 1-60 1-61 1-62 1-63 Residual silver amount (mq/dm 2 none 0.06 0.06 0.06 Color restoration ratio 100 100 i00 51 63 88 0.06 99 0.06 100 0.06 100 0.06 100 0.06 100 0.06 100 0.12 84 0.12 96 0.13 100 0.12 100 0.11 100 0.12 100 0.12 100 0.12 100 0.13 100 0.32 100 0.31 100 0.32 100 0.30 100 0.32 100 0.33 100 0.32 100 0.33 100 0.32 100 ^-vY-I II uI CI iy-±LUy-L cigei- may oe used, it necessary. Useful antifungal agents may include

A

36 As is apparent from the results in Table 2, those processed in the alkali bath of pH 8.0 or more after the bleach-fixing processig show markedly good effect of improvement in desilverizability and color restoration badness of cyan dyes.

As to the relation with pH of the bleach-fixing solution, it is seen that particularly preferable results are obtained when pH is 6 to 8. Also, when pH of the alkali bath is 9.0 of more, preferable results are shown.

Example 2 An alkali bath solution having the following composition was prepared.

[Alkali solution] Diethylenetriaminepentaacetic acid 2.0 g Buffering agent (kind is indicated in Table 3) 10 g Bleach-fixing solution in Example 1 100 ml Made up to 1 t with addition of water, and adjusted to pH as shown in Table 3.) By use of the above alkali bath solution, the same experiment and estimation as in Example 1 were made except for employing the bleach-fixing solution of pH Further, the alkali bath solution was stored in a glass 2 beaker with an opening area of 15 cm (opening area per one liter of alkali bath) at 50 °C for 5 days and days, respectively, and thereafter the same processing as above was conducted by use of the respective stored alkali bath solutions, and deterioration after storage with lapse of time of the alkali bath solution was observed. The results are also shown in Table 3.

Table 3 Experimental Buffering agent Alkali bath pH Color restoration ratio No. before storage after storage at 50 C 0 day 5 days 10 days 2-1 (Comp.) Potassium carbonate 7.0 46 48 2-2 (Inve.) Potassium carbonate 8.0 79 82 2-3 Patassium carbonate 9.0 92 95 94 2-4 Potassium carbonate 10.0 99 100 98 Potassium carbonate 12.0 100 100 100 2-6 Potassium bicarbonate 10.0 97 95 92 2-7 Boric acid 10.0 98 95 91 2-8 Borax 10.0 97 94 2-9 Sodium metaborate 10.0 96 95 93 2-10 Sodium phosphate 10.0 93 91 88 2-11 Triethanolamine 10.0 97 91 86 2-12 Diethanolamine 10.0 97 90 2-13 Sulfosalicylic acid 10.0 96 93 2-14 (Comp.) None (only KOH) 10.0 92 75 91 lubricant, image stabilizer, surfactant, color 38 As is apparent from the results in Table 3, in all of the experiments No. 2 2 to 2 13 by use of the alkali bath of the present invention, improvement effect of color restoration badness can be markedly seen also after l.,pse of time, while in the comparative experiment No. 2 1 by use of an alkali bath with less than pH 8.0 is great in color restoration badness regardless of presence or absence of storage. Also, it can be understood that, in the comparative experiment No. 2 14 in which no buffering agent is used, although pH may be adjusted to 10.0, the improvement effect of color restoration ratio can be satisfactory immediately after preparation of the alkali bath, but the color restoration will become insufficient with lapse of time, whereby no stable photographic image can be obtained.

Example 3 The processing steps in Example i, namely the respective steps of 1. color developing, 2.

bleach-fixing, 3. alkali bath and 4. stabilizing were replaced with the processing steps as shown in the following Table 4-1 and 4-2 to carry out experiments.

o o Table 4-1 Experimental 3-1 3-2 3-3 3-4 3-5 3-6 3-7 No. (Camp.) (Camp.) (Camp2.) (Inv.) (Inv.) (Inv.) (Inv.) Steps Color deve- 3 min. 3 min. 3 min. 3 min. 3 min. 3 min. 3 min.

loping 15 sec. 15 sec. 15 sec. 15 sec. 15 sec. 15 sec. 15 sec.

Bleaching 3 mmn. -1 min. 3 min. I min. 1 min.

Bleach-fixing -4 min. 3 min. -4 min. 3 min. 1 min.

Fixing 3 min. 3 min. -2 min.

Water washing 2 min. 2 min. 2 Alkali bath 1 min. 1 min. 1 min. 1 min.

Alkali bath 1 min. 1 min. 1 min. I min.

Stabilization 1 min. I min. 1 min. 1 min. 1 min. I min. I min.

Modsom 4'I-rOL.lcnlioropenyl)- 3 3 -(2 4 tdi-t-amylphenoxyacetamido)beneneamido]-5p~ 40 Table 4-2 Experimental 3-8 Experimental 3-9 No. (This inv.) No.- (This inv.) Steps Steps Color deve- 3 min.15 sec. Color deve- 3 min.15 sec.

loping loping Bleach-fixing 1 min. Fixing 1 min.

Bleaching 1 min. Bleaching 1 min.

Fixing 2 min. Bleach-fixing 2 min.

Water washing Water wasing Alkali bath 1 min. Alkali bath 1 min.

Alkali bath 1 min. Alkali bath 1 min.

Stabilization 1 min. Stabilization 1 min.

In the processing solutions used in the above processing steps, the bleach-fixing solution used was that of pH in Example 1, and the alkali bath used was similarly tht of pH 10.0.

Further, except for the bleaching solution and the fixing solution shown below, all are the same as in Example 1.

[Bleaching solution] Ammonium ethylenediaminetetraacetate Ferric diammonium ethylenediaminetetraacetate 2.0 g 100 g Ammonium bromide 130 Mercaptobenztriazole 1.5 Ammonia water 5.0 (made up to one liter with addition of water, and adjusted to pH 6.0 with ammonia wate or acetic acid) g g ml Similarly as in Example 1, ferric diammonium ethylenediaminetetraacetate was reduced with silver powder to 35 Layer lu..nlgn senav.L±.Ly u- v emulsion layer containing 1.2 g of a high 41 give 40 g of ferrous diammonium ethylenediaminetetraacetate.

[Fixing solution] Sodium sulfite 10 g Aqueous ammonium thiosulfate solution 200 ml Sodium bisulfite 5.0 g (made up to one liter with addition of water, and adjusted to pH 0 Except for the above processing steps, the same experiments as in Example 1 were conducted and color restoration ratio and desilverizability were examined.

The results are shown in Table Table Experimental No. Color restoration ratio 3-1 (Comparativa) 82 3-2 62 3-3 3-4 (This invention) 100 3-5 99 3-6 100 3-7 100 3-8 100 3-9 100 Remarks: as to residual silver amount, occured.

no problem As is apparent from Table 5, it can be appreciated that color restoration badness can be remarkably improved by Y 35 Sodium nyarogein Potassium sulfite 5.0 g

F.

42 application of the alkali bath processing of the present invention, even when desilverization processing may be variously changed.

Example 4 In the above Example 1, pH of the bleach-fixing solution was changed to 6.5, pH of the alkali bath to 10.0, and further the ferric complex of the aminopolycarboxylic aicd or aminopolyphosphonic acid shown in the following Table 6 was used in place of ferric diammonium ethylenediaminetetraacetate as the aminopolycarboxylic acid in the bleach-fixing solution at the concentration shown in Table 6, and experiments were conducted following otherwise the same procedure as in Example 1.

The results are also shown in Table 6.

Borax 2.0 g (made up to one liter with addition of water, and pH was I- I. I~ 43 Table 6 Experi- Ferric complex of Density Residual Color mental compounds of the (g/liter) silver restration No. formula amount 2 amount or (II) (mq/dm 4-1 A 8 40 0.03 74 4-2 A 8 60 0.06 86 4-3 A 8 80 none 92 4-4 A 8 100 none 100 A 8 120 none 100 4-6 A 8 140 none 100 4-7 A 8 160 none 100 4-8 A 8 200 none 100 4-9 A 8 150 none 100 4-10 A 8 150 none 100 4-11 A 13 150 none 100 4-12 A 16 150 none 98 4-13 A 17 150 none 99 4-14 A 19 150 none 100 4-15 A 22 150 none 100 4-16 A 24 150 none 100 4-17 A 26 150 none 100 4-18 A 3 150 none 98 4-19 A 15 150 none 94 4-20 A 11 150 none 94 4-21 A 32 150 none 94 44 Ps is apparent from the results in Table 6, it can be appreciated that the effect of the present invention can be obtained even if the kind and the concentration of the bleaching agent used in the bleach-fixing solution may be varied.

Example In the experiment No. 4-1 in Example 4, further the additive shown in the following Table 7 was added in an amount of 10 g per 1 liter of the alkali bath, and the experiments were conducted following otherwise the same procedure. The results are also shown in Table 7.

o 5 I k 1-32 1-33 ri 1, 7. U 10.0 11.0 45 Table 7 Additives Experimental No.

5-1 5-2 5-3 5-4 5-6 5-7 5-8 5-9 5-10C 5-11 '5-12 5-13 5-14 Sodium ferric ethylenediamine tetraacetate Sodium ferric diethylenetriaminepentaacetate Sodium ferric cyclohexanediaminetetraacetate Sodium ferric hydroxyiminodiacetate Sodium ferric glycoletherdiaminetetraacetate Hydrogene p .'oxide (36 aqueous solution) Potassium persulfate Sodium carbonate (3/2 H202) Sodium borate H202 Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Cyclohexanediaminetetraacetic acid Hydroxyiminodiacetic acid Glycoletherdiaminetetraacetic acid Residual silver amount (mg/dm none none none none none none 0.08 0.08 0.08 0.08 none none none none Color restoration ratio(%) 99 100 99 98 100 100 100 100 100 100 100 100 100 100

L;

46 As is apparent from the results in Table 7, it can be appreciated-that, when a chelating agent with a stabilization constant with iron of 6 or more is contained in the alkali bath in the processing method of the present invention, and also when the ferric complex of the compound of the present invention is contained at a certain concentration, or higher, and further when an oxidizing agent is contained, the improvement effects of color restoration badness can be further marked, respectively.

Example 6 In Example 1, the light-sensitive materials shown in the following Table 8 with various film thicknesses of the light-sensitive materials to be processed (film thickness was changed by varying only gelatin amount) and coated silver amounts, and the experiments were conducted following otherwise the same procedure as in the experiment No. 1 24. However, experiments were also conducted for comparison ,'sing no alkali bath. The results are also shoTn in Table 8.

f 47 Table 8 Experimental Light-sensitive Residual Color No. material silver restora- Film Coated sil- amount 2 tion thickness ver amount 2 (mg/dm ratio (Um) (mg/100 cm 6-1 6-2 No 6-3 alkali 6-4 bath (Compa- 6-6 rative) 6-7 Alkali 6-8 bath 6-9 pH 11.0 6-10 (This 6-11 inven- 6-12 tion) 6-13 No 6-14 alkali 6-15 bath 6-16 (Compa- 6-17 rative) Alkali 6-18 bath 6-19 pH 11.0 6-20 (This 6-21 inven- 6-22 tion) 10 60 none 13 60 none 16 60 none 20 60 none 25 60 none 30 60 none 10 60 none 13 60 none 16 60 none 20 60 none 25 60 none 30 60 none 25 20 none 25 40 none 25 60 none 25 80 none 25 100 none 25 20 none 25 40 none 25 60 none 25 80 none 25 100 none 84 72 61 41 22 14 100 100 98 98 96 96 89 22 16 8 100 100 99 92 89 1-31 88 1-32 99 1-33 100 4 4 48 As is apparent from the results in Table 8, in the processing method of the present invention, the effect is not greatly affected by the film thickness of the light-sensitive material and the coated silver amount, and good effect of color restoration badness improvement can be obtained at a film thickness of 13 u.m or more (color restoration badness is small at a film thickness of 13 uLm or less). It can be appreciated that particularly great improvement effect can be obtained in the case of a film thickness of 16um or more, while greater improvement effect can be obtained as the coated silver amount is more.

Example 7 In the following example a photographic material containing thereon 20 mg or more of silver per 100 cm 2 of the surface area of the support was processed in accordance with the method of the present invention or with the processing solution of the present invention as per Example 6.

In the Experiment, the cyan dye density (Dm C) of the maximum density max portion of the processed film sample was also measured by means of model photoelectric densitometer (produced by Konica Corporation)(as described on page 33, lines 5 and 6).

D C represents the sensitivity of a photographic film to be exposed to max light and processed.

LMM/1300y 48A Table 8 (Cont'd) Light-sensitive material Residual Color Experimental silver restora- Dmax

C

No. Film Coated sil- amount tion thickness ver amount (mg/dm 2 ratio (4m) (ma/100 cm 2 7-1 25 9.3 none 95 0.46 7-2 No 25 15 none 93 0.59 7-3 alkali 25 20 none 89 0.94 7-4 bath 25 25 none 72 1.02 (Compa- 25 30 none 65 1.07 7-6 rative) 25 40 none 60 1.21 7-7 25 60 none 22 0.48 7-8 25 70 none 19 0.43 7-9 25 80 none 16 0.40 7-10 25 100 none 8 0.20 Alkali 7-11 bath 25 9.3 none 100 0.48 7-12 pH 11.0* 25 15 none 100 0.63 7-13 Alkali 25 20 none 100 1.12 7-14 bath 25 25 none 100 1.42 7-15 pH 11.0 25 30 none 100 1.65 7-16 (This 25 40 none 100 2.01 7-17 inven- 25 60 none 99 2.18 7-18 tion) 25 70 none 98 2.23 7-19 25 80 none 92 2.26 7-20 25 100 none 89 2.26 comparative This Example clearly illustrates the superior effects which can be obtained when the photgraphic material containing thereon 20 mg or more of silver per 100 cm 2 of the surface area of the support is processed by the method of the present invention or with the processing solution of the present invention.

LMM/1 300y

Claims (18)

1. A method for processing a light-sensitive silver halide color photographic material, which comprises subjecting an exposed light-sensitive silver halide color photographic material having silver on a support thereof in an amount of 20 mg or more per 100 cm 2 of the surface area of the support, to color developing processing and then applying at least desilverization processing, characterized in that the processing bath to be used in said desilverization processing contains a ferric complex of at least one compound selected from the compounds represented by the formula and the formula (II) shown below, and after said desilverization processing, processing with an alkali bath having a pH of 8.0 or more and containing a buffering agent is performed, Formula I R L L L R 3 IN N L N 0 L L R 2 2 L 4 R 4 6 Formula II SL~R- R R 5 N L 6 R 6 o oo L 7 7 wherein L represents an alkylen Jp, a cycloalkylene group, a phenylene group, -L 8 -0-L 8 -0-L 8 L. -L 9 -Z-L 9 where Z represents "N-L 10 -N-L1- N- N-R10 or -N-L13-N- 11i I 10 I 1 -L -R L-RR R -L 1

2-R 9 L 12 -R 9 R11 1 L 1 to L 13 each represent an alkylene group; R 1 to R 1 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt); with proviso that at least two of R 1 and R 4 are carboxylic LMM/1300y 50 acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R 5 to R 7 is a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt). 2. The method for processing a light-sensitive silver halide color photographic material according to Claim 1, wherein the pH of the alkali processing solution is within the range of 8.5 to 12.0.

3. The method for processing a light-sensitive silver or C\i n 2- halide color photographic material according to Claim 1, wherein said compounds represented by the formula and the formula (II) is at least one of compounds shown below: A-1 Ethylenediaminetetraacetic acid A-2 Disodium ethylenediaminetetraacetate A-3 Diammonium ethylenediaminetetraacetate A-8 Ammonium diethylenetriaminepentaacetate A-13 Ammonium propylenediaminetetraacetate A-14 Disodium propylenediaminetetraacetate A-17 Cyclohexanediaminetetraacetic acid A-18 Disodium cyclohexanediaminetetraacetate A-19 Iminodiacetic acid A-22 Glycol ether diaminetetraacetic acid A-24 Ammonium 1,2-diaminopropanetetraacetate Sodium 1,2-diaminopropanetetraacetate A-26 Ammonium hydroxyiminodiacetate A-27 Sodium hydroxyiminodiacetate.

4. The method for processing a light-sensitive silver P one -C2 C C S' .7 k halide color photographic material according to 1a/, wherein said compounds represented by the formula and the formula (II) is contained in a solution having bleaching ability in an amount of 0.05 to 2 mol per 1 PQ zI Y 41 i14 PA- f- -51- liter of said solution. The method for processing a light-sensitive silver halide color photographic material according to Claim 4, wherein said compounds represented by the formula Pnd the formula (II) is contained in a solution having bleaching ability in an amount of 0.2 to 0.6 mol per 1 liter of said solution.

6. The method for processing a light-sensitive silver Zltl or CP Ci\oklvs -VO halide color photographic material according to Clai wherein said buffering agent is at least one of inorganic salts, amines, amino acids and organic compounds. i 15 7. The method for processing a light-sensitive silver halide color photographic material according to Claim 6, wherein the buffering agent is at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, boric acid, borax, sodium metaborate, sodium phosphate, potassium phosphate, sodium primary phosphate, ethanolamine, ethylenediamine, methylamine, trimethylamine, propylamine, hydroxyproline, leucine, glycine, alanine, aspartic acid, y-aminobutylacetic acid, sulfosalicylic acid, piperazine and guanidine.

8. The method for processing a light-sensitive silver halide color photographic material according to Claim 7, Swherein the buffering agent is at least one of sodium carbonate, potassium carbonate, potassium bicarbonate, boric acid, borax, sodium metaborate, sodium phosphate, potassium phosphate, sodium primary phosphate and sulfosalicylic acid.

9. The method for processing a light-sensitive silver halide color photographic material according to Clai i i s^ Similarly as in Example 1, ferric diammonium ethylene- diaminetetraacetate was reduced with silver powder to 52 wherein the buffering agent contained in an amount ranging from 0.2 to 50 g per one liter of the alkali bath.

10. The method for processing a light-sensitive silver Cfn\- one- of Ci;rS v t halide color photographic material according to Claim l wherein the alkali processing solution contains a chelating agent with a chelate stability constant with iron ions (logKMA) of 6 or more in the alkali processing solution.

11. The method for processing a light-sensitive silver halide color photographic material according to Claim wherein the chelating agent is at least one of ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethlvlethylenediaminetriacetic acid, dihydroxyethylglycine, ethlenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylimino- diacetic acid, diaminopropanolteraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediamine- tetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene- 1,1-diphosphonic acid, 1,l-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-l,2,4-tricarboxylic acid, l-hydroxy-l-phosphonopropane-l,2,3-tricarboxylic acid, acid, sodium pyrophosphate, sodium tetrapolyphosphate and sodium hexametaphosphate.

12. The method for processing a light-sensitive silver halide color photographic material according to Claim 11, wherein the chelating agent is at least one of 35 diaminopropanetetraacetic acid, diethylenetriaminepenta- D o\ acetic acid, hydroxyethyliminodiacetic acid, diamino- i! f, As is apparent from Table 5, it can be appreciated that color restoration badness can be remarkably improved by 53 propanoltetraacetic acid and ethylenediaminetetraacetic thereof. acid and salts

13. The method for processing a light-sensitive silver halide color photographic material according to any one of Claims 10 to 12, wherein the chelating agent is contained in an amount ranging from 0.01 to 50 g.

14. The method for processing a light-sensitive silver halide color photographic material according to any one of Claims 1 to 13, wherein the alkali processing solution contains 1 x 10 3 mol or more of ferric complex of an aminopolycarboxylic acid per 1 liter of the alkali processing solution. The method for processing a light-sensitive silver halide color photographic material according to any one of Claims 1 to 14, wherein the alkali processing solution contains an oxidizing agent.

16. The method for processing a light-sensitive silver halid color S photographic material according to Claim 15, wherein the oxidizing agent is at least one of hydrogen peroxide, sodium percarbonate, sodium perborate, potassium persulfate, ammonium persulfate, sodium perchlorate, sodium .oo hypochlorite, potassium hydrobromide, ammonium hydrobromide and sodium hydrobromide.

17. The method for processing a photographic material according to oxidizing agent is contained in an of the alkali processing solution.

18. The method for processing a photographic material according to amount of silver on the support is mg/100 cm 2 of the support. light-sensitive silver halide color Claim 15 or Claim 16, wherein the amount ranging from 0.01 g to 30 g/liter light-sensitive silver halide color any one of Claims 1 to 17, wherein the within the range of 30 mg/100 cm 2 to

19. A processing solution for light-sensitive silver halide color photographic material, which is an alkali processing solution to be used after an exposed light-sensitive silver halide color photographic material LMM/1300y ,i Mt 54 having silver on a support thereof in an amount of 20 mg or more per 100 cm 2 of the surface area of the support, is subjected to color developing processing and desilverization processing by use of a fe-t: complex of at least one compound selected from the compounds represented by the formula and the formula (II) shown below, said alkali processing solution having a pH of 8.0 or more and containing a buffering agent, Formula I RI L-NL3 R 3 R -L L L 4 -R R2 2 4 R 4 Formula II L6 R6 R- L NR S 7 7 wherein L represents an alkylene group, a cycloalkylene group, a phenyien- group, -L -0-L -0-L or -L 9 -Z-L 9 where Z represents >N-L 10 -R 8 1 N 'N-RIO or -yN-L N -L 12 -R 9 L 12 -R 9 R 11 R 11 L1 to L 13 each represent an alkylene group; R 1 to R11 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt); with proviso that at least two of R 1 and R4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R 5 to R 7 is a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt). The method for processing a light-sensitive silver halide color photographic material according to Claim 19, wherein the pH of the alkali processing solution is within the range of 8.5 to 12.0.

21. A method for processing a light-sensitive silver halide color photographic material, which method is substantially as herein described L; I 00y 'V LMM/II00y 55 with reference to Example 1 and any of experiments 1-3 to 1-9, 1-12 to 1-18, 1-21 to 1-27, 1-30 to 1-36, 1-39 to 1-45, 1-48 to 1-54 or 1-57 to 1-63, Example 2 and any one of experiments 2-2 to 2-13, Example 3 and any one of experiments 3-4 to 3-9, Example 4 and any one of experiments 4-1 to 4-21, Example 5 and any one of experiments 5-1 to 5-14, or Example 6 and any one of experiments 6-9 to 6-12 or 6-18 to 6-22.

22. A processing solution for light-sensitive silver halide color photographic material which is an alkali processing solution to be used after an exposed light-sensitive silver halide color photographic material is subjected to color developing processing and desilverization processing with use of a ferric complex of Formula I and Formula II as defined in Claim 20, substantially as herein described with reference to Example 1 and any of experiments 1-3 to 1-9, 1-12 to 1-18, 1-21 to 1-27, 1-30 to 1-36, 1-39 to 1-45, 1-48 to 1-54 or 1-57 to 1-63, Example 2 and any one of experiments 2-2 to 2-13, Example 3 and any one of experiments 3-4 to 3-9, Example 4 and any one of experiments 4-1 to 4-21, Example 5 and any one of experiments 5-1 to 5-14, or Example 6 and any one of experiments 6-9 to 6-12 or 6-18 to 6-22. DATED this TWENTY-FIFTH day oF MARCH 1991 Konica Corporation Patent Attorneys for the Applicant SPRUSON FERGUSON M s 4 4 i i LMM/1300y I A