EP0436947B1 - Solution de développement pour un matériau photographique en couleurs à l'halogénure d'argent sensible à la lumière et méthode de traitement - Google Patents

Solution de développement pour un matériau photographique en couleurs à l'halogénure d'argent sensible à la lumière et méthode de traitement Download PDF

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EP0436947B1
EP0436947B1 EP90125712A EP90125712A EP0436947B1 EP 0436947 B1 EP0436947 B1 EP 0436947B1 EP 90125712 A EP90125712 A EP 90125712A EP 90125712 A EP90125712 A EP 90125712A EP 0436947 B1 EP0436947 B1 EP 0436947B1
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Prior art keywords
solution
color developing
developing solution
group
acid
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English (en)
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EP0436947A1 (fr
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Yutaka C/O Konica Corporation Ueda
Shigeharu C/O Konica Corporation Koboshi
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • This invention relates to a color developing solution for a light-sensitive silver halide color photographic material and a processing method using the same, more specifically, it relates to a color developing solution for a light-sensitive silver halide color photographic material capable cf obtaining stable photographic characteristics even when the sulfite concentration of the color developing solution is low and overcome the problems of generation of contamination caused at a transport rack in a color developing processing tank or a roller portion, and a processing method using the same.
  • Processings of a light-sensitive material basically comprise two steps of color developing and desilvering, and the desilvering comprises a bleaching and a fixing step or a bleach-fixing step.
  • the additional processing steps a rinsing processing, stabilizing processing, etc. may be added.
  • silver halide developed becomes silver by reduction and simultaneously an aromatic primary amine developing agent oxidized reacts with a coupler to form a dye.
  • a halide ion generated by reduction of the silver halide is dissolved in a developing solution and accumulated therein.
  • a component such as a restrainer contained in a light-sensitive silver halide photographic material is also dissolved and accumulated in the color developing solution.
  • silver generated by developing is bleached by an oxidizing agent, and all the silver salts are removed away from the light-sensitive photographic material by a fixing agent as a soluble silver salt.
  • a one-bath bleach-fixing processing step in which the bleaching step and the fixing step are carried out simultaneously has also been known.
  • a development inhibiting substance is accumulated in a developing solution by effecting developing processing of a light-sensitive photographic material as mentioned above.
  • a color developing agent and benzyl alcohol are consumed or brought of by accumulating in the light-sensitive photographic material to be processed whereby concentrations of these components are gradually lowered. Accordingly, in the developing processing method in which a large amount of light-sensitive silver halide photographic material is continuously processed by using an automatic developing machine, it is required to have a means for maintaining components of a color developing solution in a constant concentration range in order to avoid fluctuation of development finished characteristics due to change in concentrations of the components.
  • a method of replenishing a replenishing solution in order to replenish lacked components and to dilute unnecessary components increased is generally employed.
  • replenishing the replenishing solution a large amount of overflow is necessarily generated and disposed, so that this method causes great problems in view of economic and pollution. Therefore, in recent years, in order to decrease the above mentioned overflow solution, there have been proposed a regenerating method of a developing solution by an ion exchange resin method or an electrodialysis method, a concentrated less-replenishing method, or the method in which a regenerating agent is added to the overflow solution and the resulting solution is used again as a replenishing solution, and have been practiced.
  • Regeneration of a developing solution is carried out by removing bromide which is an unnecessary accumulated component and replenishing a consumed component.
  • this method (the ion exchange resin method and the electrodialysis method) has a defect that developing processing characteristics of the light-sensitive material are lost unless the composition of a developing solution should be determined by a chemical analysis and made constant, thus, it is substantially impossible to introduce the method in a small-sized photofinishing laboratory or mini-laberatory not having specific skill since complicated controls thereof are required.
  • the concentrated less-replenishing method is a particularly suitable method for a small-sized laboratory since a novel device is not specifically required and processing controls are easy.
  • this method also has some defects.
  • dissolved-out materials from a light-sensitive material into a developing solution are accumulated with a great extent and decomposition products of components in the color developing solution due to air oxidation are also accumulated with a large amount.
  • contamination at a rack or roller portion in the color developing processing tank of an automatic developing machine is generated so that a trouble of contaminating a light-sensitive material to be processed by the contamination is generated.
  • either of the methods does not have drastic effect and there are problems that one of them is insufficient in preventing deterioration at a white ground, or limited in a used amount because bad effect is caused in photographic performances so that effects are insufficient, or sludge is generated.
  • EP-A-0 312 984 discloses a method of processing high chloride photographic materials with a color-developing solution which is substantially free from sulfite ions and whose replenishing rate is less than or equal to 20 ml/m 2 .
  • the color developer contains at least one aromatic primary amine color-developing agent.
  • Surface active agents may be added. This document, however, does not disclose mixed polyoxyalkylene oxides or esters and amines for use as water-soluble surfactants.
  • EP-A-0 273 986 discloses a method of rapidly developing a photographic material, in which method the presence of sulfite is preferably excluded.
  • Surfactants can be added as development accelerators. However, the specific surfactants as defined in present claim 1 are not disclosed in this document.
  • EP-A-0 411 513 describes a method of processing a color-photographic material in a color developer containing an anionic surface-active agent, which is present in an amount of from 0.01 to 10 g/l.
  • the document is a document according to Article 54(3) EPC. The specific surfactants defined in present claim 1 are not described in this document.
  • JP-A-55018675 it is disclosed that addition of anionic or amphoteric surfactants and an antifoamer to a color developer composition can prevent occurence of tarry insoluble matter and eliminate foaming tendency in preparation of a developing solution.
  • US-A-4,232,112 teaches that a combination of aryl sulfonic acids with a whitening agent selected from 4,4'-diaminostilbenedisulfonic acid derivatives can supress formation of color stain on white portions upon reduced replenishment rates or high speed processing.
  • objects of the present invention are firstly to provide a color developing solution which is capable of effecting rapid processing and can provide stable photographic performances and a processing method, and secondly to provide a color developing solution which causes less contamination due to deposition or adhesion of powder-like material (sludge) to a rack or a roller whereby causing less contamination of a light-sensitive material and a processing method.
  • a color developing solution which is capable of effecting rapid processing and can provide stable photographic performances and a processing method
  • a color developing solution which causes less contamination due to deposition or adhesion of powder-like material (sludge) to a rack or a roller whereby causing less contamination of a light-sensitive material and a processing method.
  • a color developing solution for a light-sensitive silver halide color photographic material comprises a sulfite concentration of 1.0 x 10 -3 mole or less per liter of the color developing solution and containing 0.5 g/l to 20 g/l of a water-soluble surfactant selected from the compounds as defined in claim 1.
  • said water-soluble surfactant is contained in an amount of 1.0 g to 10 g per liter of the color developing solution.
  • a processing method of a light-sensitive silver halide color photographic material comprises processing the light-sensitive silver halide color photographic material with a color developing solution after imagewise exposure, the improvement wherein said color developing solution according to claim 1 is used.
  • said water-soluble surfactant is contained in an amount of 1.0 g to 10 g per liter of the color developing solution and said surfactant contains the surfactant represented by the above formula (I).
  • a replenishing amount of said color developing solution is 120 ml or less per 1 m 2 of the light-sensitive silver halide color photographic material.
  • the water-soluble surfactant herein mentioned in the present specification means the water-soluble, having two groups of hydrophilic and hydrophobic groups which are opposed to each other in solubility to a solvent.
  • the water-soluble surfactant is classified into an ionic surfactant and a nonionic surfactant by the reason that it shows ionic property in an aqueous solution or not, and the ionic surfactant is further classified into an anionic surfactant, a cationic surfactant and an amphoteric surfactant according to a kind of ion species at a portion of showing surface activity.
  • these kinds of surfactants those as defined in claim 1 can be used in order to accomplish the objects of the present invention and two or more thereof may be used in combination.
  • the water-soluble surfactant can be selected from the group consisting of I - 1 C 12 H 25 COO( ⁇ C 2 H 4 O) ⁇ 10 -H I - 2 C 9 H 19 COO( ⁇ C 2 H 4 O) ⁇ 4 -H I - 3 C 12 H 25 NH( ⁇ C 2 H 4 O) ⁇ 10 -H I - 4 C 12 H 25 NH( ⁇ C 2 H 4 O) ⁇ 15 -H I - 6 C 12 H 25 NHCH 2 CH 2 OH
  • a 2 represents a monovalent organic group selected from an alkyl group having 6 to 50, preferably 6 to 35 carbon atoms (e.g. each group of hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) and an aryl group substituted by an alkyl group having 3 to 35 carbcn atoms or by an alkenyl group having 2 to 35 carbon atoms.
  • an alkyl group having 6 to 50 preferably 6 to 35 carbon atoms (e.g. each group of hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) and an aryl group substituted by an alkyl group having 3 to 35 carbcn atoms or by an alkenyl group having 2 to 35 carbon atoms.
  • an alkyl group having 1 to 18 carbon atoms e.g. unsubstituted alkyl group such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl
  • a substituted alkyl group such as benzyl and phenethyl
  • an alkenyl group having 2 to 20 carbon atoms e.g. unsubstituted alkenyl groups such as oleyl, cetyl and allyl, and substituted alkenyl groups such as styryl.
  • aryl group there may be mentioned each group of phenyl, biphenyl and naphthyl, and preferably a phenyl group.
  • position to be substituted on the aryl group either of ortho, meta or para may be substituted and plural number of groups may be substituted.
  • B or C represents ethylene oxide or propylene oxide, or where n 1 , m 1 and l 1 each represent 0, 1, 2 or 3. m and n each represent an integer of 0 to 100.
  • X 1 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and for example, there may be mentioned groups as explained in A 2 .
  • An amount of the water-soluble surfactant to be used in the color developing solution of the present invention is 0.5 to 20 g/l, preferably 1.0 to 15 g/l. If it is less than 0.5 g/l, remarkable effect of the present invention in the color developing solution with low sulfite concentration cannot be expected, while if it exceeds 20 g, foam will likely be caused so that it is not practical.
  • the water-soluble surfactant is contained in an amount of 0.5 to 20 g per liter of the color developing solution and it may be 0.5 to 20 g including the surfactant dissolved out from a light-sensitive silver halide color photographic material, but in order to accomplish the effect of the present invention as mentioned above, it is particularly preferred to previously add the above amount in the color developing solution. That is, the water-soluble surfactant dissolved out from a light-sensitive material is accumulated in the color developing solution according to the continuous processing while it is a small amount, but the effect thereof is markedly different from the case wherein it is previously added in the color developing solution.
  • the water-soluble surfactant to be used in the present invention should be contained at least one kind, but it may be contained 2 or more in combination, in summary, it is sufficient so long as it is contained in an amount of 0.5 to 20 g per liter of the color developing solution.
  • the water-soluble surfactant to be used in the present invention is a compound represented by the formula (I)-1 to (I)-25 or (II), most preferably the compound represented by the formula (I)-1 to (I)-25.
  • the compound represented by the formula (I)-1 to (I)-25 scarcely affects the developing property and it shows less foaming property so that it can be used in a large amount. As the results, the effects of the present invention becomes more marked which is one of the preferred embodiments of the present Invention.
  • the anionic surfactant When the cationic surfactant is added in the color developing solution, depositions sometimes occur during continuous processing, the anionic surfactant is relatively low in solubility and the nonionic surfactant causes less problems mentioned above.
  • an amount of the sulfurous acid (or sulfite) to be used in the present invention is 1 x 10 -3 mole/liter or less, preferably 0, the effect of the present invention is remarkable.
  • the sulfite concentration is preferably substantially 0 in view of developability, but in order to prevent oxidation of the color developing solution for making kits, it may be added in a small amount of 1.0 x 10 -3 mole/liter or less.
  • a substance generally called as a builder can be used in combination.
  • the builder there may be mentioned an inorganic builder represented by carbonates such as sodium carbonate and sodium bicarbonate, silicates such as sodium metasilicate, sodium orthosilicate and sodium sesquisilicate, and phosphate such as sodium pyrophosphate, sodium tripolyphosphate and sodium tetraphosphate, and an organic builder represented by carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and carboxymethyl starch. Any of the builders may be used, but in order to accomplish the effect of the present invention, the organic builder is preferably used. It has been known that a solution containing a surfactant generally foams, but in the case of a processing solution for photography, foaming phenomenon causes many inconvenient problem so that a defoaming agent may be used, if necessary.
  • an organic preservative such as hydroxylamine derivatives described in Japanese Provisional Patent Publications No. 146043/1988, No. 146042/1988, No. 146041/1988, No. 146040/ 1988, No. 135938/1988 and No. 118748/1988, hydroxamic acids, hydazides, phenols, ⁇ -hydroxyketones, ⁇ -aminoketones, saccharides, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamides and fused ring system amines as described in Japanese Provisional Patent Publication No.
  • 62639/1989 can be preferably used. Particularly, it is preferred to add the compound represented by the following formula (A) and hydrazines for rapid processing and deminishing bluing. Also, by employing the above compounds, precipitation of crystals at the surface of the color developing solution becomes good and other effects can be accomplished so that it can be mentioned as one of the preferred embodiments of the present invention.
  • R 1 and R 2 each represent an alkyl group or a hydrogen atom, provided that both of R 1 and R 2 do not represent hydrogen atoms at the same time. Also, R 1 and R 2 may be formed a ring combinedly.
  • R 1 and R 2 each represents an alkyl group or a hydrogen atom both of which are not hydrogen atoms at the same time, and the alkyl group represented by R 1 and R 2 may be the same or different, and an alkyl group having 1 to 3 carbon atom is preferred.
  • the alkyl group of R 1 and R 2 may include those having a substituent, and R 1 and R 2 may be combined to form a ring and also form a heterocyclic ring such as piperidine or morpholine.
  • These compounds are used generally in the form of a free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate or acetate.
  • a concentration of the compound represented by the formula (A) in the color developing solution is generally 0.2 g/l to 50 g/l, preferably 0.5 g/l to 30 g/l, more preferably 1 g/l to 15 g/l.
  • a hydroxylamine conventionally used and the aforesaid organic preservative may be used in combination with-the compound represented by the formula (A), but preferably not using the hydroxylamine in view of developability.
  • a compound represented by the following formula is preferably added since air oxidation resistance of the solution can be improved and even if it is mixed in a bleach-fixing solution, no bad effect occurs.
  • R21 represents a hydroxyalkyl group having 2 to 6 carbon atoms
  • R 22 and R 23 each represent a hydrogen atom, an alkyl group having 1 to 6 cabron atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a group represented by where n 1 is an integer of 1 to 6,
  • X' and Y' each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.
  • the compound represented by the above formula (B) is preferably used in an amount of 1 g to 100 g, more preferably 2 g to 30 g per liter of the color developing solution in view of prevention of air oxidation.
  • the color developing agent to be used in the color developing solution of the present invention is preferably a p-phenylenediamine type compound having a water-soluble group and the water-soluble group is possesed at least one on an amino group or a benzene nucleus of the p-phenylenediamine compound.
  • Specific water-soluble group may include: -(CH 2 )n-CH 2 OH, -(CH 2 ) m -NHSO 2 -(CH 2 ) n -CH 3 , -(CH 2 ) m -O-(CH 2 ) n -CH 3 , -(CH 2 CH 2 O) n -C m H 2m+1 (wherein m and n each represent an integer of 0 or more), -COOH group and -SO 3 H group.
  • Exemplary compounds of the color developing agent to be preferably used in the present invention are enumerated below.
  • color developing agent exemplified above, preferred in the present invention are compounds represented by Exemplary No. (A - 1), (A - 2), (A - 3), (A - 4), (A - 6), (A - 7) and (A - 15), and particularly preferred is No. (A - 1).
  • the above color developing agent is generally used in the form of a salt such as hydrochloride, sulfate and p-toluenesulfonate.
  • an amount of the p-phenylenediamine type compounds having a water-soluble group to be preferably used in the present invention is 0.5 x 10 -2 mole or more, more preferably 1.0 x 10 -2 to 1.0 x 10 -1 mole per liter of the color developing solution.
  • the following components for the developing solution may be contained in addition to the above components.
  • sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate and borax may be used alone or in combination of two or more in the range where no deposition is generated and pH stabilization effect can be maintained.
  • various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borates may be used.
  • inorganic and organic antifoggants may be added.
  • a development accelerator may be used.
  • the development accelerator there may be mentioned various kinds of pyridinium compounds specifically disclosed in U.S. Patents No. 2,648,604 and No. 3,671,247, and Japanese Patent Publication No. 9503/1969, or other cationic compound, a cationic dye such as phenosaphranine, a neutral salt such as thallium nitrate, polyethylene glycol or derivatives thereof as disclosed in U.S. Patents No. 2,533,990, No. 2,531,832, No. 2,950,970 and No. 2,577,127 and Japanese Patent Publication No.
  • a nonionic compound such as polythioethers, also a phenethyl alcohol as disclosed in U.S. Patent No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine and amines.
  • Benzyl alcohol is not preferably used in the present invention and as for an organic solvent with poor solubility represented by phenethyl alcohol, it is desired to not use it in view of accomplishing the object of the present invention effectively. If it is used, tar is likely caused by the use for a long period of term of the color developing solution, particularly in low replenishing system. Generation of such tar sometimes causes serious defect that commercial value is markedly impaired by adhering to a paper light-sensitive material to be processed.
  • the organic solvent with poor solubility is bad in solubility to water so that troublesome of requiring a stirring device for preparation of the color developing solution itself. Further, even if such a stirring device is used, development accelerating effect is limited due to its bad solibility.
  • an orgnic solvent with poor solubility has problems that a pollution loading value such as biochemical oxygen demand (BOD) is large so that it cannot be disposed in a sewer or a river and for its waste liquor processing, many labour and costs are required. Therefore, not only benzyl alcohol but also other organic solvent with poor solubility are preferably reduced or eliminated their amount used.
  • BOD biochemical oxygen demand
  • a triazinylstylbene type optical brightening agent is preferably added.
  • triazinylstylbene type optical brightening agent that represented by the following formula is preferred.
  • X 2 , X 3 , Y 1 and Y 2 each represent a hydroxyl group, a halogen atom such as chlorine and bromine, an alkyl group (e.g. methyl and ethyl), an aryl group (e.g. phenyl and methoxyphenyl), or -OR 25 .
  • R 21 and R 22 each represent a hydrogen atom, an alkyl group which may have a substituent(s), or an aryl group which may have a substituent(s)
  • R 23 and R 24 each represent an alkylene group which may have a substituent(s)
  • R 25 represents a hydrogen atom, an alkyl group which may have a substituent(s) or an aryl group which may have a substituent(s)
  • M represents a cation (e.g. sodium, potassium, lithium and ammonium).
  • the alkyl groups represented by R 21 , R 22 and R 25 are preferably those having 1 to 6 carbon atoms and the alkylene groups represented by R 23 and R 24 are preferably those having 1 to 2 carbon atoms.
  • a hydroxyl group, a sulfo group, a sulfoamino group and a carboxyamino group are preferred.
  • Specific examples of may include an amino group, an alkylamino group (e g. methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, ⁇ -hydroxyethylamino, di( ⁇ -hydroxyethyl)amino, amino, ⁇ -sulfoethylamino, N-( ⁇ -sulfoethyl)-N'-methylamino and N-( ⁇ -hydroxyethyl-N'-methylamino), and an arylamino group (e.g.
  • an alkylamino group e g. methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, ⁇ -hydroxyethylamino, di( ⁇ -hydroxyethyl)amino, amino, ⁇ -sulfoethylamino, N-( ⁇ -sulfoe
  • alkoxy group e.g. methoxy, ethoxy and methoxyethoxy
  • aryloxy group e.g. phenoxy and p-sulfophenoxy
  • preferred compounds are those wherein all the X 2 , X 3 , Y 1 and Y 2 are or -OR 25 and most preferred compound is that wherein one of X 3 and Y 1 is -OR 25 and the other is and one of X 3 and Y 2 is -OR 25 , the other is
  • the triazinylstilbene type brightening agent to be preferably used in the present invention can be synthesized by the conventional method as described in, for example, "Optical Brightening agent” edited by Chemical Products Industry Association (published in August, 1976), p. 8.
  • E - 34 particularly preferably used are E - 34, E - 35, E - 36, E - 37 and E - 42.
  • the triazinylstilbene type brightening agent is preferably added in an amount of 0.2 g to 6 g, more preferably in the range of 0.4 g to 3 g per liter of the color developing solution.
  • ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, ⁇ -cyclodextrin, and other compounds as disclosed in Japanese Patent Publications No. 33378/1972 and No. 9509/1969 as an organic solvent for increasing solubility of the color developing agent.
  • an auxiliary developer may be used in combination with the color developing agent.
  • the auxiliary developer there have been known, for example, N-methyl-p-aminophenolsulfate (Metol), phenidone, N,N'-diethyl-p-aminophenol hydrochloride and N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride, and as an amount thereof to be added, 0.01 g to 1.0 g per liter of the color developing solution is generally preferred.
  • additives such as stain preventives, sludge preventives and interlayer effect accelerating agents may be used.
  • the color developing solution of the present invention can be prepared by adding the above respective components successively to a predetermined amount of water and stirring.
  • a component(s) having low solubility to water may be added by mixing with the above organic solvent such as triethanol amine.
  • a condensed aqueous solution or a solid in which a plural number of components can be stably existed, respectively, is previously prepared in a small apparatus and added in water and the mixture is stirred to prepare the color developing solution of the present invention
  • the above color developing solution can be used in an optional pH range, but in view of rapid processing, it is preferred to use in a pH of 9.5 to 13.0, more preferably a pH of 9.8 to 12.0.
  • the processing temperature is generally 30 °C or higher, preferably 33 °C or higher, particularly preferably 35 °C to 65 °C, and the processing time is preferably within 90 seconds, more preferably 3 sec to 60 sec, particularly preferably 3 sec to 45 sec.
  • the effect of the present invention can be effectively accomplished when the system is low replenishing so that the replenishing amount of the color developing solution is preferably 120 ml/m 2 or less, more preferably 110 ml/m 2 or less, particularly preferably 100 ml/m 2 or less.
  • various processing systems can be employed including one bath treatment, and other various methods such as a spray system in which a processing solution is atomized, a web system using a carrier in which a processing solution is impregnated to contact therewith, or a developing method due to a viscous processing solution.
  • an organic acid ferric complex salt such as aminopolycarboxylic acid is used and as an organic acid constituting said organic acid ferric complex salt may preferably include an amonocarboxylic acid type compound and aminophosphonic acid type compound, and each represents an amino compound having at least one carboxylic acid group and an amino compound having at least one phosphonic acid group, more preferably the compounds represented by the following formulae (1) and (2).
  • E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R 55 OR 55 OR 55 - or -R 55 ZR 55 - where Z represents >N-R 55 -A 5 or >N-A5, R 51 to R 55 each represent a substituted or unsubstituted alkylene group, A 1 to A 5 each represent a hydrogen atom, -OH, -COOM or -PO 3 M 2 where M represents a hydrogen atom or an alkali metal atom.
  • aminocarboxylic acid type compounds and aminophosphonic acid type compounds compounds which are particularly preferably used in view of accomplishing the effect of the present invention are (1 - 1), (1 - 2), (1 - 4), (1 - 5), (1 - 6), (1 - 7), (1 - 8), (1 - 10), (1 - 19), (2 - 1), 12 - 3) and (2 - 5).
  • aminocarboxylic acid type compounds and aminophosphonic acid type compounds particularly preferred are (1 - 1), (1 - 2), (1 - 4), (1 - 6), (1 - 8) and (1 - 10) since they are high bleaching abilizy and rapid processing.
  • ferric complex salts may be used at least one, but may be used in combination of two or more.
  • bleaching agent is preferably used in an amount of 5 to 450 g/l, more preferably 20 to 250 g/l. From the viewpoint of rapid processing and stain prevention, it is particularly preferred to use 60 g/l or more, most preferably 80 g/l to 250 g/l.
  • a silver halide fixing agent may be added in addition to the bleaching agent as mentioned above and, if necessary, a solution having a composition containing a sulfite as a preservative may be applied.
  • halide in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide and ammonium iodide may be used.
  • the silver halide fixing agent as mentioned above to be contained in the bleaching solution or the bleach-fixing solution there may be specifically mentioned a compound which forms a water-soluble complex reacting with silver halide to be used in the usual fixing processing, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. Also, ammonium salts are effective since they have rapid diffusion rate.
  • These fixing agents are used in an amount of 5 g/l or more to an amount within the range of capable of being dissolved, and generally 50 g/l to 250 g/l. In the point of rapid processing, 70 g/l to 250 g/l is preferred.
  • various buffering agent such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide may be added singly or in combination of two or more.
  • optical brightening agents or defoaming agents may be contained.
  • preservatives such as bisulfite adducts of hydroxylamine, hydrazine and aldehyde compound, an organic solvent such as methanol, dimethylsulfoamide and dimethylsulfoxide can be optionally added.
  • a pH of the bleach-fixing solution to be used is generally in the range of 4.0 to 9.5, desirably 4.5 to 8.5, and most preferably 5.0 to 8.0. In the case of the bleaching solution, it is preferably into 7.0, more preferably 1.5 to 6.0, particularly preferably 2.0 to 5.5.
  • a pH of the fixing solution is preferably 5.0 to 9.0, more preferably 5.5 to 8.5.
  • a temperature of the processing is 80 °C or lower, desirably 35 °C to 70 °C while depressing evaporation. If it exceeds 70 °C, it is not preferred in view of dryness, while if it is less than 35 °C, it is also not preferred in view of rapid processing.
  • a processing time of the bleaching or bleach-fixing is preferably 2 sec to 50 sec, more preferably 3 sec to 40 sec, most preferably 5 sec to 30 sec.
  • a fixing processing time is preferably 5 sec to 3 min, more preferably 7 sec to 2 min.
  • a sulfite is preferably contained.
  • Said sulfite is not limited either an organic compound or an inorganic compound so long as it releases a sulfite ion, but preferably an inorganic salt.
  • Preferred specific examples thereof may include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite.
  • the above sulfite is preferably added to the stabilizing solution in an amount of at least 1 x 10 -3 mole/liter, more preferably to be added in an amount of 5 x 10 -3 mole/liter to 10 -1 mole/liter whereby the effect of the present invention, particularly stain preventive effect becomes remarkable and such an embodiment is preferably used in the present invention.
  • it may be added directly to the stabilizing solution, but to add it to a stabilizing replenishing solution is preferred.
  • ammonium hydroxide ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium fluoride, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium, nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium laurintricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate
  • An amount of the ammonium compound to be added is preferably in the range of 0.001 mole to 1.0 mole, more preferably in the range of 0.002 mole to 2.0 mole per liter of the stabilizing solution.
  • the stabilizing solution it is preferred to contain a chelating agent having a chelate stability constant of 8 or more to accomplish the object of the present invention.
  • the chelate stability constant is a well known constant by, for example, written by L.G. Sillen & A.E. Martell, "Stability constants of Metal-ion Complexes", The Chemical Society, London (1964), and written by S.Chaberek & A.E. Martell, "Organic Sequestering Agents", Wiley (1959).
  • the following compounds may be mentioned, but not limited by these. That is, there may be mentioned ethylenediaminediorthohydroxyphenylacetic acid, diaminpropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycin, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycoletherdiaminetetraaceiic acid, ethylenediaminetetraxismethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic
  • polyvinylpyrrolidone PVP K-15, K-30 and K-90, all trade names
  • organic acid salts salt of citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid
  • pH adjusting agents phosphates, borates, hydrochloric acid and sulfuric acid
  • mildewproofing agents phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, cyabendazole derivatives, organic halide compounds, and other mildewproofing agents which have been known as a slime controller for paper-pulp industry
  • optical brightening agents surfactants, antiseptic agents, metal salts of a metal such as Bi, Mg, Zn, Ni, Al, Sn, Ti and Zr.
  • These compounds may be optionally used in either of combinations thereof so long as causing any bad effect against stability of a color photographic image during preservation and occurrence of deposition
  • the processing temperature for the stabilizing processing is 15 °C to 70 °C, preferably in the range of 20 °C to 55 °C. Also, a processing time is preferably 120 sec or shorter, more preferably 3 sec to 90 sec, most preferably 6 sec to 50 sec whereby the effect of the present invention can be accomplished more effectively
  • washing processing is not entirely required, but rinse or surface washing with a small amount of water within extremely minute time can be optionally carried out, if necessary. It is preferred to exist a soluble iron salt in the stabilizing solution to accomplish the effect of the present invention.
  • inorganic iron salts such as ferric chloride, ferrous chloride, ferric phosphate, ferric bromide, ferric nitrate and ferrous nitrate
  • organic acid iron salts such as ferric ethylenediaminetetraacetate, ferric 1-hydroxyethylidene-1,1-diphosphonate, ferrous 1-hydroxyethylidene-1,1-diphosphonate, ferrous ethylenediaminetetraacetate, ferric diethylenetriaminepentaacetate, ferrous diethylenetriaminepentaacetate, ferric citrate, ferric ethylenediaminetetramethylenephosphonate, ferrous ethylenediaminetetramethylenephosphonate, ferric nitrilotrimethylenephosphonate, ferric nitrilotriacetate and ferrous nitrilotriacetate.
  • These organic acid iron salts may be either a free acid type or a sodium salt, a potassium salt, an ammonium salt, a lithium salt or an alkylammonium salt (triethanolammonium salt, trimethylammonium salt or tetramethylammonium salt).
  • These soluble iron salts are preferably used in a concentration of at least 5 x 10 -3 mole/liter, more preferably in the range of 8 x 10 -3 to 150 x 10 -3 mole/titer, further preferably in the range of 12 x 10 -3 to 100 x 10 -3 mole/liter in the stabilizing solution.
  • these soluble iron salts may be added to the stabilizing solution (tank solution) by adding in a replenishing solution for the stabilizing solution, or may be added to the stabilizing solution (tank solution) by dissolving out from a light-sensitive material in the stabilizing solution, or may be added to the stabilizing solution (tank solution) by adhering to a light-sensitive material from the previous bath and bring it into the stabilizing solution tank.
  • a stabilizing solution which is made a calcium ion or magnesium ion concentration 5 ppm or less by subjecting to treatment by using an ion exchange resin may be used, or it may be used by further adding the above antiseptic agent or halogen ion releasing compound.
  • the pH of the stabilizing solution is preferably in the range of 5.5 to 10.0.
  • a pH adjusting agent which may be contained in the stabilizing solution may be any of an alkali agent or an acid agent generally known.
  • the amount to be replenished of the stabilizing solution is preferably 0.1- to 50-fold, particularly preferably 0.5- to 30-fold of the amount brought in from the previous bath (bleach-fixing solution) per unit area of a light-sensitive material in the points of rapid processing and preservability of a dye image.
  • the stabilizing tank for stabilizing processing is preferably 1 to 5 tanks, particularly preferably 1 to 3 tanks, most preferably 1 tank in view of desilvering property and rapid processing.
  • Silver halide grains to be preferably used in the light-sensitive material are silver halide grains composed mainly of silver chloride containing at least 80 mole % or more of silver chloride, more preferably 90 mole % or more, particularly preferably 95 mole % or more, most preferably 99 mole % or more. By having such a composition, good effects can be obtained with respect to rapid processing and prevention of stain so that it is preferred embodiment of the present invention to process the light-sensitive material using silver halide emulsion composed mainly of silver chloride.
  • the above silver halide emulsion composed mainly of silver chloride may contain silver bromide and/or silver iodide as a silver halide composition, and in this case, an amount of silver bromide is preferably 20 mole % or less, more preferably 10 mole % or less, further preferably 3 mole % or less, and also when silver iodide exists, it is preferably 1 mole % or less, more preferably 0.5 mole % or less, most preferably 0.
  • the silver halide grains composed mainly of silver chloride with 80 mole % or more of silver chloride may be applied to at least one layer of silver halide emulsion layers, but preferably they are applied to all of the silver halide emulsion layers.
  • the silver halide emulsion layer of the light-sensitive material to be processed by the present invention contains a color coupler.
  • 2-equivalent coupler is particularly preferred.
  • Couplers are disclosed, for example, in the following publications: "Color coupler” written by W. Pelz in Research Report by Agfa (Mitanderlnausden Anlagenslaboratorien der Agfa), Leverkusaen/München, Vol. III. p. 111 (1961); "The chemistry of Synthetic Dyes” written by K. Venkataraman, Vol. 4, pp. 341 to 387, Academic Press; “The Theory of the Photographic Process", 4th Edition, pp. 353 to 362; and “Research Disclosure", No. 17643, Section VII.
  • 5-pyrazolone type and pyrazoloazole type compounds disclosed in U.S. Patents No. 4,310,619 and No. 4,351,897, European Patent No. 73,636, Research Disclosures No. 24220 and No. 24230, Japanese Provisional Patent Publication No. 43659/1985 and WO 88/04795 are preferred, and particularly, to use the magenta coupler represented by the formula (M - 1) described at page 26 of Japanese Provisional Patent Publication No. 106655/1988 (as the specific exemplary magenta couplers thereof, those of No. 1 to No. 77 described at pages 29 to 34 of Japanese Provisional Patent Publication No.
  • nitrogen-containing heterocyclic mercapto compounds may include (I' - 1) to (I' - 87) described at pages 42 to 45 of Japanese Provisional Patent Publication No. 106655/1988.
  • any of the light-sensitive material which is processed by the so-called inner type development system, which light-sensitive material contains a coupler therein may be used and the color developing solution can be applied to optional light-sensitive material such as a color paper, a color negative film, a color positive film , a color reversal film for slide, a color reversal film for movie, a color reversal film for television and a reversal color paper, but most preferably to apply it to a color paper composed mainly of silver chloride.
  • a color developing solution which is capable of effecting rapid processing and stable in photographic performances, and a processing method can be provided. Also, a color developing solution which is less contamination at a rack or roller portion due to deposition or adhesion of sludge and easy in maintenance and a processing method can be provided.
  • each layer having a constitution as mentioned below was coated to prepare a multi-layer light-sensitive silver halide color photographic material (1).
  • the coating solutions are prepared as shown below.
  • a high boiling point organic solvent DNP
  • 26.7 g of a yellow coupler Y - 1
  • 10.0 g of a dye image stabilizer ST - 1
  • 6.67 g of the same ST - 2
  • 0.67 g of an additive HQ - 1
  • the solution was emulsified in 220 ml of a 10 % gelatin aqueous solution containing 7 ml of a 20 % surfactant (SU - 1) by using an ultrasonic homogenizer to prepare a yellow coupler dispersion.
  • This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared by the following conditions to prepare a first layer coating solution.
  • the second layer to the seventh layer coating solutions are also prepared in the same manner as in the above first layer coating solution.
  • DOP Dioctylphthalate DNP Dinonylphthalate DIDP Diisodecylphthalate PVP Polyvinylpyrrolidone
  • control of the pAg was carried out according to the method described in Japanese Provisional Patent Publication No. 45437/1984, and control of the pH was carried out by using an aqueous solution of sulfuric acid and sodium hydroxide.
  • EMP - 1 was subjected chemical ripenning at 50 °C for 90 minutes by using the following compounds to obtain a blue-sensitive silver halide emulsion (Em A).
  • Em A blue-sensitive silver halide emulsion
  • Sodium thiosulfate 0.8 mg/mole AgX
  • Chloroauric acid 0.5 mg/mole AgX Stabilizer SB - 5 6 x 10 -4 mole/mole AgX
  • Sensitizing dye D - 1 4.3 x 10 -4 mole/mole AgX " D - 4 0.7 x 10 -4 mole/mole AgX
  • EMP - 2 was subjected chemical ripenning at 55 °C for 120 minutes by using the following compounds to obtain a blue-sensitive silver halide emulsion (Em B).
  • Em B blue-sensitive silver halide emulsion
  • Chloroauric acid 1.0 mg/mole AgX Stabilizer SB - 5 6 x 10 -4 mole/mole AgX Sensitizing dye D - 2 4 x 10 -4 mole/mole AgX
  • Processing steps (1) Color development 35.0 ⁇ 0.3 °C 45 sec (2) Bleach-fixing 35.0 ⁇ 0.5 °C 45 sec (3) Stabilizing (3 tanks cascade) 30 to 34 °C 90 sec (4) Drying 60 to 80 °C 30 sec (Color developing tank solution)
  • the running processing was carried out by filling the above color developing solution in an automatic processor and also filling the bleach-fixing tank solution and the stabilizing solution, and while processing the above color paper sample and supplementing the above color developing replenishing solution, the bleach-fixing replenishing solution and the stabilizing replenishing solution through a quantitative pump every 3 minutes interval.
  • a replenishing amount in the color developing tank 100 ml thereof was replenished per 1 m 2 of the color paper, as a replenishing amount in the bleach-fixing tank, 220 ml of the bleach-fixing replenishing solution and as a replenishing amount in the stabilizing tank, 250 ml of the stabilizing replenishing solution, respectively.
  • the running processing was carried out until an amount of the color developing solution replenished in the color developing tank solution became 3-times of the volume of the color developing tank solution with a continuous processing of 0.05R per day.
  • 1R herein mentioned means that the color developing replenishing solution was replenished with the same amount as the color developing tank volume.
  • the tank solution was divided and 2.5 g of the water-soluble surfactant shown in Table 1 was added per liter of the solution and stain at the unexposed portion and crystallization property were evaluated.
  • the stain at the unexposed portion was obtained by measuring spectral reflective densities at 440 nm and 640 nm to determine difference in densities before and after addition of the surfactant. It shows that the larger density difference is, the more marked in improved effect of stain is.
  • crystallization property the solution was placed in a narrow-mouthed bottle (with ground glass) having an opening area of 10 cm 2 and stored at normal temperature for 10 days while effecting evaporation correction every day whereby crystallization property was evaluated. Provided that the evaluation of the crystallization property was carried out as shown below.
  • Example 1 The same processings as in Example 1 were carried out except that the color developing tank solution and color developing replenishing solution in Example 1 were changed to those as shown below, respectively, and the surfactants shown in Table 2 were added thereto, and contamination at a rack or roller and stain at the unexposed portion were evaluated in the same methods as in Example 1.
  • the water-soluble surfactant used in the present invention clearly has an amount dependency to the effects of the present invention, and when it is added with an amount of 0.5 g or more, preferably 1.0 g or more, marked effects can be obtained. Particularly, the effects are remarkable when the water-soluble surfactant represented by the formula (I) is added.
  • Example 2 By using the same color paper as in Example 1 and the same processing solutions as in Example 2, the running processing was carried out in the same manner as in Example 1 except for using the compounds shown in Table 3 as the water-soluble surfactant to be added to the color developing tank solution and the replenishing solution therefor, and changing the sulfite concentration of the color developing tank solution and the replenishing solution therefor as shown in Table 3, contamination at a rack or roller in the color developing tank of the automatic developer, stain at the unexposed portion and developability after termination of said running processing were evaluated.
  • Table 3 the compounds shown in Table 3 as the water-soluble surfactant to be added to the color developing tank solution and the replenishing solution therefor
  • the maximum spectral reflective density of blue at the sulfite concentration of 0 was measured as 100, and the stain at the unexposed portion was measured from the density difference from the reflective density at no surfactant and the sulfite concentration of 0.
  • the results are shown in Table 3.
  • Example 3 the surfactants described in Example 1 were also investigated and substantially the effects could be obtained.
  • Example 2 By using the same color paper as in Example 1 and the same processing solutions as in Example 2, the running processing was carried out in the same manner as in Example 1 except for fixedly using the water-soluble surfactant to be added in the color developing tank solution and replenishing solution therefor to the exemplary compound II - 36 and changing a replenishing amount to the color developing tank to those shown in Table 4, contamination at a rack or roller portion in the color developing tank of the automatic developer, and stain at the unexposed portion were evaluated in the same manner as in Example 2.
  • Example 5 When a concentration of the color developing agent in Example 5 was increased to 6.5, 8.0 and 10.0 g, respectively, stain at the unexposed portion becomes large. However, when the surfactant of the present invention was used, improved effect in stain at the unexposed portion becomes remarkable. This tendency is the same as in the surfactant used in Example 1.
  • Example 2 By using the same color paper as in Example 1 and the same processing solutions as in Example 2, the running processing was carried out in the same manner as in Example 1 except for fixedly using the water-soluble surfactant to be added in the color developing tank solution and replenishing solution therefor to the exemplary compound I - 23 and changing color developing processing conditions to those shown in Table 5, contamination at a rack or roller portion in the color developing tank of the automatic developer, and stain at the unexposed portion were evaluated in the same manner as in Example 2. (Color developing processing solution) Processing steps Color developing processing time Color developing temperature (1) 3 min 33 °C (2) 1 min 35 °C (3) 45 sec 35 °C (4) 20 sec 39 °C
  • a paper support laminated with a polyethylene on the both surfaces thereof were provided the following layers to prepare a multi-layer color printing paper having the following layer constitution.
  • the coating solutions were prepared as shown below.
  • an emulsion was prepared by effecting sulfur sensitization and gold sensitization after adding two kinds of the blue-sensitive sensitizing dyes (D - 5 and D - 6) shown below to silver bromide emulsion (cubic with grain size of 0.83 ⁇ m and variation coefficient of 0.05, which contains 1 mole % of silver bromide based on the whole grain at part of the grain surface localized).
  • the above emulsified dispersion and the emulsion were mixed and dissolved, and the first layer coating solution was prepared so as to have a composition as shown below.
  • Coating solutions for the second to the seventh layers were also prepared in the same manner as in the preparation of the first layer coating solution.
  • the following compound was added in an amount of 2.5 x 10-3 mole per mole of silver halide.
  • 1-(5-methylureidophenyl)-5-mercaptotetrazole was added in amounts of 8.0 x 10 -5 mole, 8.0 x 10 -4 mole and 2.0 x 10 -4 mole, per mole of silver halide, respectively.
  • the irradiation preventive dye As the irradiation preventive dye, the following were used.
  • compositions of each layer were shown.
  • the numeral shows a coating amount (g/m 2 ).
  • An amount of the silver halide emulsion is shown with a coated amount calculated in terms of silver.
  • Second layer Silver bromide emulsion mentioned above 0.35 Gelatin 1.85 Yellow coupler (Y - 2) 0.80 ST - 6 0.20 ST - 7 0.05 Solvent (Sol - 4) 0.35 Second layer Gelatin 1.00 HQ - 1 0.09 Solvent (Sol - 5) 0.20 Solvent (Sol - 6) 0.05 Third layer Silver bromide emulsion (cubic with grain size of 0.45 ⁇ m and variation coefficient of 0.10, which contains 1 mole % of silver bromide based on the whole grain at part of the grain surface localized) 0.25 Gelatin 1.25 M - 2 0.30 ST - 8 0.10 ST - 9 0.05 Solvent (Sol - 7) 0.30 Solvent (Sol - 8) 0.15 Fourth layer Gelatin 1.50 UV - 3 0.50 HQ - 1 0.05 Solvent (Sol - 8) 0.15 Fourth layer Gelatin 1.50 UV - 3 0.50 HQ - 1 0.05 Solvent (Sol - 8) 0.15 Fourth layer Gelatin 1.50
  • Example 5 The same evaluations were carried out in the same manner as in Example 5 except for changing the magenta coupler M - 1 used in Example 1 to the magenta couplers M - 2 to M - 11 and Comparative magenta couplers MR - 1 and MR - 2 mentioned below, respectively, or changing the cyan couplers C - 1 and C - 2 to C - 58, C - 76, C - 83 in the exemplary compounds mentioned at pages 76 to 124 of Japanese Patent Application No. 92655/1986, or CC - 9 and Comparative cyan couplers CCR - 1 and CCR - 2 in the exemplary compounds mentioned at pages 81 to 85 of the same, respectively.
  • samples of the present invention showed values 20 to 30 % lower in each of magenta stain and cyan stain than the comparative ones.
  • Example 6 In the same manner as in Example 1 except for using the compounds shown in Table 6 instead of N,N-diethylhydroxylamine in the color developing tank solution and the replenishing solution in Example 1, processing was carried out to evaluate the contamination at the rack and roller portions and stain at the unexposed portion in the same manner as in Example 1. As for the stain at the unexposed portion, evaluation was carried out by measuring spectral reflective densities at 440 nm and 640 nm. The results are shown in Table 6. Table 6 Experiment No.
  • Example 1 In the same manner as in Example 1 except for adding the compounds shown in Table 7 to the color developing tank solution and the replenishing solution, processing was carried out as in Example 1 to evaluate the contamination at the rack and roller portions and stain at the unexposed portion in the same manner as in Example 1. As for the stain at the unexposed portion, evaluation was carried out by measuring spectral reflective densities at 440 nm and 640 nm. The results are shown in Table 8. Table 7 Experiment No.

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Claims (8)

  1. Solution de développement chromogène pour un matériau photographique en couleur à base d'halogénure d'argent sensible à la lumière qui comprend une concentration en sulfite de 1,0 x 10-3 mole ou moins par litre de la solution de développement chromogène et contenant 0,5 à 20 g/l d'un dérivé tensio-actif soluble dans l'eau, dans laquelle ledit dérivé tensio-actif soluble dans l'eau est choisi dans le groupe comprenant

            I - 1    C12H25COO(̵C2H4O)̵10-H



            I - 2    C9H19COO(̵C2H4O)̵4-H



            I - 3    C12H25NH(̵C2H4O)̵10-H



            I - 4    C12H25NH(̵C2H4O)̵15-H

    Figure imgb0240

            I - 6   C12H25NHCH2CH2OH

    Figure imgb0241
    Figure imgb0242
    Figure imgb0243
    Figure imgb0244
    Figure imgb0245
    Figure imgb0246
    Figure imgb0247
    Figure imgb0248
    Figure imgb0249
    Figure imgb0250
    Figure imgb0251
    Figure imgb0252
    Figure imgb0253
    Figure imgb0254
    Figure imgb0255
    Figure imgb0256
    Figure imgb0257
    Figure imgb0258
    Figure imgb0259
     et
    Figure imgb0260
     dans laquelle A2 représente un groupe organique monovalent choisi parmi un groupe alkyle ayant 6 à 50 atomes de carbone et un groupe aryle substitué par un groupe alkyle ayant 3 à 35 atomes de carbone ou par un groupe alcényle ayant 2 à 35 atomes de carbone; B ou C représente l'oxyde d'éthylène ou l'oxyde de propylène ou
    Figure imgb0261
     où n1 , m1 et ℓ1 représentent chacun 0, 1, 2 ou 3; m et n représentent chacun un nombre entier valant de 0 à 100; X1 représente un atome d'hydrogène, un groupe alkyle, un groupe aralkyle ou un groupe aryle.
  2. Solution selon la revendication 1, dans laquelle la quantité dudit dérivé tensio-actif soluble dans l'eau est de 1,0 à 10 g par litre de la solution de développement chromogène.
  3. Solution selon la revendication 1 ou 2, dans laquelle ladite solution contient en outre un agent d'azurage optique de type triazinylstilbéne représenté par la formule suivante:
    Figure imgb0262
     dans laquelle X2, X3, Y1 et Y2 représentent chacun un groupe hydroxyle, un atome d'halogène tel qu'un atome de chlore et de brome, un groupe alkyle, un groupe aryle,
    Figure imgb0263
     ou -OR25, où R21 et R22 représentent chacun un atome d'hydrogène, un groupe alkyle qui peut avoir un ou des substituants, ou un groupe aryle substitué ou non substitué, R23 et R24 représentent chacun un groupe alkylène substitué ou non substitué, R25 représente un atome d'hydrogène, un groupe alkyle substitué ou non substitué ou un groupe aryle substitué ou non substitué, et M représente un cation.
  4. Procédé de traitement d'un matériau photographique en couleur à base d'halogénure d'argent sensible à la lumière qui comprend le traitement du matériau photographique en couleur à base d'halogénure d'argent sensible à la lumière avec une solution de développement chromogène après l'exposition selon l'image, caractérisé en ce qu'on utilise une solution de développement chromogène selon la revendication 1.
  5. Procédé selon la revendication 4, dans lequel la quantité dudit dérivé tensio-actif soluble dans l'eau est de 1,0 g à 10 g par litre de la solution de développement chromogène.
  6. Procédé selon la revendication 4 ou 5, dans lequel la quantité d'alimentation de ladite solution de développement chromogène est de 120 ml ou moins pour 1 m2 de matériau photographique en couleur à base d'halogénure d'argent sensible à la lumière.
  7. Procédé selon l'une quelconque des revendications 4, 5 ou 6, dans lequel ladite solution de développement chromogène contient en outre un agent d'azurage optique de type triazinylstilbéne tel que défini dans la revendication 3.
  8. Solution selon la revendication 1, dans laquelle A2 représente un groupe alkyle ayant 6 à 35 atomes de carbone.
EP90125712A 1989-12-28 1990-12-28 Solution de développement pour un matériau photographique en couleurs à l'halogénure d'argent sensible à la lumière et méthode de traitement Expired - Lifetime EP0436947B1 (fr)

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JP2887714B2 (ja) * 1992-06-03 1999-04-26 富士写真フイルム株式会社 カラー現像液およびそれを用いた処理方法
US5972573A (en) * 1997-04-15 1999-10-26 Konica Corporation Image forming method
US6497475B1 (en) 1999-09-03 2002-12-24 Canon Kabushiki Kaisha Liquid discharge method, head, and apparatus which suppress bubble growth at the upstream side
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DE69031026D1 (de) 1997-08-14
DE69031026T2 (de) 1997-10-30
JP2915095B2 (ja) 1999-07-05
EP0436947A1 (fr) 1991-07-17
JPH03223757A (ja) 1991-10-02

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