EP0450293A2 - Solution de blanchiment pour matériau d'halogÀ©nure d'argent pour la photographie en couleurs et procédé de traitement en utilisant la même - Google Patents

Solution de blanchiment pour matériau d'halogÀ©nure d'argent pour la photographie en couleurs et procédé de traitement en utilisant la même Download PDF

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Publication number
EP0450293A2
EP0450293A2 EP91102316A EP91102316A EP0450293A2 EP 0450293 A2 EP0450293 A2 EP 0450293A2 EP 91102316 A EP91102316 A EP 91102316A EP 91102316 A EP91102316 A EP 91102316A EP 0450293 A2 EP0450293 A2 EP 0450293A2
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Prior art keywords
group
solution
silver halide
mole
bleaching
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EP91102316A
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German (de)
English (en)
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EP0450293A3 (en
Inventor
Masao Ishikawa
Shigeharu Koboshi
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0450293A2 publication Critical patent/EP0450293A2/fr
Publication of EP0450293A3 publication Critical patent/EP0450293A3/en
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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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • This invention relates to a bleaching solution for a light-sensitive silver halide color photographic material and a processing method using said bleaching solution, more particularly to a bleaching solution for a light-sensitive silver halide color photographic material by which bleaching fog can be effectively inhibited, and a processing method using said bleaching solution.
  • a processing of a light-sensitive material basically comprises two steps of color developing and desilvering, and desilvering comprises bleaching and fixing steps or a bleach-fixing step. As other additional processing steps than these steps, a rinsing processing and a stabilizing processing are added.
  • inorganic oxidizing agents such as prussiate and bichromate have been widely used.
  • a processing solution containing as an oxidizing agent a metal complex salt of an organic acid such as a metal complex salt of an aminopolycarboxylic acid has been used.
  • the processing solution using a metal complex salt of an organic acid has a poor oxidizing power, and therefore has a drawback that a bleaching rate (oxidizing rate) of image silver (metal silver) formed during a developing step is slow.
  • an iron (III) complex salt of ethylenediaminetetraacetic acid which is considered to have a strong bleaching power among metal complex salts of an aminopolycarboxylic acid has been practically utilized in part as a bleaching solution and a bleach-fixing solution.
  • a means for maintaining concentrations of respective components of a processing solution within a predetermined range is required.
  • a so-called high concentration and low replenishment system in which these replenishing solutions are concentrated and replenished in small amounts or a method in which a regenerating agent is added to an overflow solution and the solution obtained is used again as a replenishing solution.
  • a bleaching solution there has been utilized practically a method in which a ferrous organic acid complex salt generated by bleaching developed silver, for example, an iron (II) complex salt of ethylenediaminetetraacetic acid is oxidized by aeration to be converted into an iron (III) complex salt of ethylenediaminetetraacetic acid, namely, a ferric organic acid complex salt, further, a regenerating agent for supplementing insufficient components is added thereto, and the solution obtained is used again as a replenishing solution.
  • a ferrous organic acid complex salt generated by bleaching developed silver for example, an iron (II) complex salt of ethylenediaminetetraacetic acid is oxidized by aeration to be converted into an iron (III) complex salt of ethylenediaminetetraacetic acid, namely, a ferric organic acid complex salt, further, a regenerating agent for supplementing insufficient components is added thereto, and the solution obtained is used again as a replenishing solution.
  • a high concentration and low replenishment system in which low replenishment is carried out without carrying a regenerating processing is preferred.
  • concentrations of components of a color developing solution brought into a bleaching solution are elevated, and also influence of condensation due to evaporation is liable to be exerted, whereby components of a color developing solution is accumulated increasingly.
  • concentrations of components of a color developing solution in a bleaching solution are elevated, mixing ratios of a color developing agent and a sulfite which are reductive components are increased, whereby there are drawbacks that a bleaching reaction is inhibited and that as a more serious problem, bleaching fog is liable to be generated.
  • the bleaching fog has been increased in the recent low replenishment of a bleaching solution, and a trouble of tar generation in a bleaching tank of an automatic processor tends to occur.
  • a first object of the present invention is to provide a bleaching solution for a light-sensitive silver halide color photographic material which enables rapid processing and low replenishment, and yet is improved in bleaching fog, and a processing method using the same.
  • a second object of the present invention is to provide a bleaching solution for a light-sensitive silver halide color photographic material which is excellent in processing stability and enables both of continuous processing and processing of a small quantity over a long period of time, and a processing method using the same.
  • a bleaching solution for a light-sensitive silver halide color photographic material comprising at least 0.10 moIe/t of a ferric complex salt of a compound represented by the following formula (A) and ammonium ions with an amount of 50 mole % or less based on total cations, and a method for processing a light-sensitive silver halide color photographic material using said bleaching solution.
  • a 1 to A4 may be the same or different, respectively and each represent -CH 2 0H, -COOM or -PO 2 M ⁇ M 2 where M, M 1 and M 2 each represent a hydrogen atom, sodium, potassium or ammonium; and X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms and a total carbon number including a branched part is 3 or more.
  • Preferred embodiments are the above bleaching solution having a pH of 2.0 to 5.5 and the method for processing a light-sensitive silver halide color photographic material using the bleaching solution. Further, the bleaching solution in which an amount of ammonium ions is 20 mole % or less based on the total cations in the above bleaching solution and the processing method using the bleaching solution are also a preferred embodiment. Furthermore, the bleaching solution in which an amount of ammonium ions is 0 to 10 mole % or less based on the total cations in the above bleaching solution and the processing method using the bleaching solution are also a preferred embodiment of the present invention. It is a preferred embodiment that a replenishing amount of the bleaching solution is 20 to 400 ml/m 2 per 1 m 2 of a light-sensitive material since the effect of the present invention can be exhibited remarkably.
  • the bleaching solution containing a ferric complex salt of a compound represented by the formula (A) in the present invention has been known in Japanese Unexamined Patent Publication No. 222252/1987, and the fact that bleaching fog is liable to be generated has been also known in the above Japanese Publication. Further, the fact that bleaching fog can be prevented by making a pH of a bleaching solution 2.5 to 5.5 has been also known in Japanese Unexamined Patent Publication No. 44352/1990. However, in the known examples as described above, bleaching fog cannot be prevented completely by making a pH of a bleaching solution lower. When a bleaching solution is replenished with a smaller amount, further when a processing quantity is small, bleaching fog becomes more significant.
  • the present inventors have found that the above bleaching fog is liable to be generated by a bleaching power of a ferric complex salt of the formula (A) and that the bleaching fog is further liable to be generated by using a ferric complex salt together with ammonium ions, to accomplish the present invention.
  • a 1 to At may be the same or different, respectively and represent -CH 2 0H, -COOM or -PO 3 M 1 M 2 where M, M 1 and M 2 each represent a hydrogen atom, sodium, potassium or ammonium; and X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (e.g. propylene, butylene and pentamethylene).
  • substituent group there may be mentioned a hydroxyl group and a lower alkyl group having 1 to 3 carbon atoms.
  • Preferred specific examples of the compound represented by the above formula (A) are shown below.
  • a sodium salt, a potassium salt or an ammonium salt of them can be used as desired.
  • an ammonium salt of a ferric complex salt is used in an amount of 50 mole % or less, preferably 20 mole % or less, more preferably 0 to 10 mole % based on the total cations for preventing bleaching fog.
  • those particularly preferably used in the present invention are (A - 1), (A - 4), (A - 7) and (A - 8), particularly preferably (A - 1).
  • a ferric complex salt of the compound represented by the above formula (A) is used in an amount of at least 0.10 mole per liter of a bleaching solution, preferably in the range of 0.15 mole to 0.6 mole, more preferably in the range of 0.18 mole to 0.5 mole.
  • ferric complex salt of the compound represented by the above formula (A) in combination with a ferric complex salt of the compound represented by the above formula (A), other ferric complex salts of an aminopolycarboxylic acid (e.g. a ferric complex salt of ethylenediaminetetraacetic acid, a ferric complex salt of diethylenetriaminepentaacetic acid, a ferric complex salt of 1,2-cyclohexanediaminetetraacetic acid and a ferric complex salt of glycol ether diaminetetraacetic acid) can be combinedly used.
  • an aminopolycarboxylic acid e.g. a ferric complex salt of ethylenediaminetetraacetic acid, a ferric complex salt of diethylenetriaminepentaacetic acid, a ferric complex salt of 1,2-cyclohexanediaminetetraacetic acid and a ferric complex salt of glycol ether diaminetetraacetic acid
  • substantially means at least 70 % or more (calculated in terms of mole) based on all ferric complex salts. Said ratio is preferably 80 % or more, more preferably 90 % or more, most preferably 95 % or more.
  • the bleaching solution according to the present invention preferably contains imidazole and a derivative thereof or at least one compound represented by the following formulae (I) to (IX), whereby the effect of the present invention can be exhibited more favorably. Further, since another effect that precipitation caused by silver in the bleaching solution is reduced can be obtained, the above compounds are used preferably in the present invention.
  • Q represents a group of atoms necessary for forming a nitrogen-containing hetero ring (including those to which a 5 or 6-membered unsaturated ring is fused); and R 1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic group (including those to which a 5 or 6-membered unsaturated ring is fused) or an amino group.
  • R 2 and R 3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group;
  • A represents or an n 1 -valent heterocyclic residue (including those to which a 5 or 6-membered unsaturated ring is fused);
  • X' has the same meaning as X;
  • Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl group or M represents a divalent metal atom;
  • R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group,
  • the compound represented by the formula (II) may include an enolized product and a salt thereof.
  • R 6 and R 7 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B 1 -S-Z 1 ;
  • R 6 and R 7 may be bonded to form a ring;
  • Y 1 represents >N- or >CH-;
  • B 1 represents an alkylene group having 1 to 6 carbon atoms;
  • Z 1 represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue or and
  • n 7 represents an integer of 1 to 6.
  • R 8 and R 9 each represent where R 10 represents an alkyl group or -(CH 2 )n 8 SO 3 -provided that when R 10 is -(CH 2 )n 8 SO 3 - , t represents 0, and when R 10 is an alkyl group, t represents 1; G-represents an anion; and n 8 represents an integer of 1 to 6.
  • Q 1 represents a group of atoms necessary for forming a nitrogen-containing hetero ring (including those to which a 5 or 6-membered unsaturated or saturated ring is fused); and R 11 represents a hydrogen atom, an alkali metal atom, or an alkyl group where Q' has the same meaning as Q 1 .
  • D 1 , D 2 , D 3 and D 4 each represent a mere bonding arm, an alkylene group having 1 to 8 carbon atoms or a vinylene group; q 1 , q 2 , q 3 and q 4 each represent 0, 1 or 2; and a ring formed together with sulfur atoms may be further fused to a 5 or 6-membered saturated or unsaturated ring.
  • X 2 represents -COOM', -OH, -SO 3 M', -CONH 2 , -S0 2 NH 2 , -NH 2 , -SH, -CN, -CO 2 R 16 , -SO 2 R 16 , -OR 16 , -NR 16 R 17 , -SR 16 , -SO 3 R 16 , -NHCOR 16 , -NHSO 2 R 16 , -OCOR 16 or -SO 2 R 16 ;
  • Y 2 represents mg and ns each represent an integer of 1 to 10;
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 17 and R 18 each represent a hydrogen atom, a lower alkyl group, an acyl group or where R 16 represents a lower alkyl group;
  • R 19 represents -NR 2 oR21, -OR 22 or -SR 22 ;
  • R 20 and R 21 each represent a hydrogen atom or a lower alkyl
  • Ar represents a divalent aryl group or a divalent organic group in which an aryl group is combined with an oxygen atom and/or an alkylene group
  • B 2 and B 3 each represent a lower alkylene group
  • R 23 , R24, R 25 and R 26 each represent a hydroxy-substituted lower alkyl group
  • x and y each represent 0 or 1
  • G' represents an anion
  • z represents 0, 1 or 2.
  • R 29 and R 30 each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
  • R 31 represents a hydrogen atom or an alkyl group
  • R 32 represents a hydrogen atom or a carboxy group.
  • bleaching accelerators of the present invention are compounds generally used as a bleaching accelerator, and hereinafter called as the bleaching accelerators of the present invention.
  • bleaching accelerators may be used singly or in combination of two or more kinds, and the amount to be added is generally in the range of about 0.01 to 100 g per liter of the bleaching solution for obtaining good results.
  • the amount to be added is extremely small, a bleaching accelerating effect is small, and when the amount to be added is unnecessarily and extremely large, precipitation occurs, whereby a light-sensitive silver halide color photographic material processed may be stained in some cases. Accordingly, it is preferably 0.05 to 50 g, more preferably 0.05 to 15 g per liter of the bleaching solution.
  • the bleaching accelerator When the bleaching accelerator is added, it may be added as such and dissolved, but in general, it may be previously dissolved in water, an alkali or an organic acid and then added, and if necessary, it can be dissolved by using an organic solvent such as methanol, ethanol and acetone and then added.
  • an organic solvent such as methanol, ethanol and acetone
  • the bleaching solution of the present invention is preferably used at pH 2.0 to 5.5, more preferably pH 3.0 to 5.0. If the pH of the bleaching solution is more than 5.5, bleaching fog cannot be prevented sufficiently. On the other hand, if the pH is less than 2.0, bleaching fog can be prevented, but influence may be exerted on photographic performances. Processing is carried out preferably at a temperature of 20 C to 45 C, more desirably 25 °C to 42 C.
  • a halide such as ammonium bromide is generally added.
  • pH buffering agents comprising boric acid or various salts such as borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained singly or in combination of two or more kinds. Further, various fluorescent brighteners, anti- forming agents, surfactants and antifungal agents can be also contained.
  • the replenishing amount of the bleaching solution according to the present invention is preferably 20 ml to 400 ml, more preferably 30 ml to 350 ml, particularly preferably 40 ml to 300 ml, most preferably 50 ml to 250 ml per 1 m 2 of a light-sensitive silver halide color photographic material.
  • the bleaching solution described above is used immediately after color development during processing steps.
  • processing is preferably carried out by a bleaching solution and subsequently by a fixing solution or a bleach-fixing solution.
  • a so-called fixing agent is indispensable.
  • the fixing agent there may be included compounds which can form a complex salt of an aqueous solution by reacting with silver halide, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, or thiourea and thioether, preferably thiosulfates and thiocyanates.
  • thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate
  • thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate
  • thiourea and thioether preferably thiosulfates and thiocyanates.
  • 50 % or less, preferably 20 % or less of total cations in the fixing solution or the bleach-fixing solution are ammonium ions similarly as in the bleaching solution, whereby a slight effect on antistaining can be obtained.
  • pH buffering agents comprising sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite and sodium metabisulfite, boric acid, and various salts such as borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained singly or in combination of two or more kinds.
  • rehalogenating agents such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride and ammonium bromide may be desirably contained.
  • pH buffering agents such as borate, oxalate, acetate, carbonate and phosphate, and those generally known as additives in a fixing solution and a bleach-fixing solution such as alkylamines and polyethylene oxides can be added suitably.
  • the above fixing agent is used as a fixing agent in an amount of 0.1 mole or more, preferably in the range of 0.3 mole to 4 mole, particularly preferably in the range of 0.5 mole to 3.0 mole, most preferably in the range of 0.6 mole to 2.0 mole per liter of a processing solution for obtaining the effect of the present invention.
  • air or oxygen may be blown into a processing bath or a tank for storing a processing replenishing solution, if desired, or an appropriate oxidizing agent such as hydrogen peroxide, bromate and persulfate may be added suitably.
  • silver may be recovered from the fixing solution or the bleach-fixing solution according to a known method.
  • electrolysis method disclosed in French Patent No. 2,299,667
  • precipitation method disclosed in Japanese Unexamined Patent Publication No. 73037/1977 and West German Patent No. 2,331,220
  • ion exchange method disclosed in Japanese Unexamined Patent Publication No. 17114/1976 and West German Patent No. 2,548,23
  • metal substitution method disclosed in U.K. Patent No. 1,353,805.
  • an in-line silver recovery from a tank solution is particularly preferred since rapid processing suitability is further improved, but silver may be recovered from an overflow waste liquor and then used again.
  • the replenishing amount of the fixing solution and the bleach-fixing solution according to the present invention is 800 ml or less per 1 m 2 of a light-sensitive material
  • the effect of the present invention can be exhibited more favorably.
  • the amount is preferably 20 ml to 650 ml, particularly preferably 30 ml to 400 ml per 1 m 2 of a light-sensitive material, good results can be obtained.
  • an iodide (ammonium iodide, potassium iodide, sodium iodide and lithium iodide) is contained in an amount of 0.1 g/t to 10 g/ in the fixing solution and the bleach-fixing solution according to the present invention, the effect of the present invention can be further enhanced.
  • the amounts of the compounds represented by the formula (FA) and the compounds of the group of compounds (FB) to be added are each in the range of 0.1 g to 300 g, particularly in the range of 0.2 to 200 g, particularly preferably in the range of 0.5 to 150 g per liter of a processing solution.
  • a sulfite adduct is preferably used.
  • a compound which forms a stable sulfite adduct with the above sulfite ions there may be mentioned, for example, a compound having an aldehyde group, a compound containing cyclic hemiacetal, a compound having a-dicarbonyl group and a compound having a nitrile group, but compounds represented by the formulae (A-I) and (A-II) are particularly preferably used.
  • a 2 , A3, At and As each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group.
  • the alkyl group having 1 to 6 carbon atoms may include those which are straight or branched, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an n-pentyl group, an iso-pentyl group, a hexyl group and an isohexyl group, which may be substituted.
  • the substituent group there may be included specifically a formyl group (e.g.
  • each group of formylmethyl and 2-formylethyl an amino group (e.g. each group of aminomethyl and aminoethyl), a hydroxyl group (e.g. each group of hydroxymethyl, 2-hydroxyethyl and 2-hydroxypropyl), an alkoxy group (e.g. each group of methoxy and ethoxy) and a halogen atom (e.g. each group of chloromethyl, trichloromethyl and dibromomethyl).
  • the alkenyl group may be substituted or unsubstituted.
  • the unsubstituted alkenyl group may include each group of vinyl and 2-propenyl, and the substituted one may include, for example, each group of 1,2-dichloro-2-carboxyvinyl and 2-phenylvinyl.
  • sulfite adduct compounds are used preferably in an amount in the range of 0.1 g to 80 g, more preferably in the range of 0.5 g to 40 g per liter of a processing solution.
  • the processing time by the bleaching solution and a processing solution having fixing ability (the fixing solution or the bleach-fixing solution) according to the present invention is preferably 3 minutes and 45 seconds or shorter in total, and when the total processing time is preferably 20 seconds to 3 minutes and 20 seconds, more preferably 40 seconds to 3 minutes, particularly preferably in the range of 60 seconds to 2 minutes and 40 seconds, the effect of the present invention can be exhibited favorably.
  • the bleaching time can be selected as desired from within the range of the total processing time described above, but preferably 1 minute and 30 seconds or shorter, more preferably 10 seconds to 70 seconds, particularly preferably 20 seconds to 55 seconds for obtaining the effect of the present invention.
  • the processing time by the processing solution having fixing ability can be selected as desired, but preferably 3 minutes and 10 seconds or shorter, more preferably in the range of 10 seconds to 2 minutes and 40 seconds, particularly preferably in the range of 20 seconds to 2 minutes and 10 seconds for obtaining the effect of the present invention.
  • crossover time between a color developing solution tank and a bleaching solution tank is preferably within 10 seconds, particularly preferably within 7 seconds.
  • the compulsory stirring of a solution refers not to diffusional movement of a solution in general but to compulsory stirring by providing a stirring means.
  • the stirring means may include the following methods.
  • the high pressure spray processing method is a system in which processing is carried out by spraying a processing solution directly on a light-sensitive material in a processing solution from a spray nozzle by applying a pressure of a discharge pressure of 0.1 kg/cm 2 or higher
  • the spraying stirring method is a system in which processing is carried out by spraying a processing solution directly on a light-sensitive material in a processing solution from a nozzle by applying a pressure of a discharge pressure of 0.1 kg/cm 2 or higher.
  • the pressure source a pressure pump and a solution-charging pump are generally used.
  • the pressure pump there may be mentioned a plunger pump, a gear pump, a magnet pump and a cascade pump, and for example, Model 15-LPM, Model 10-BFM, Model 20-BFM and Model 25-BFM pumps, all trade names, manufactured by Maruyama Seisakusho K.K. have been known as examples thereof.
  • Model MD-30 Model MO-56, Model MDH-25 and Model MDK-32 pumps, all trade names, manufactured by Iwaki K.K.
  • the nozzle and the spray nozzle may be of straight advancing type, sector type, round type, whole surface type or round ring type, and those having a strong impact force and giving small vibrations to a light-sensitive material to be processed are effective.
  • the impact force of the spray is determined principally by a flow (t/min) and a spray pressure (kg/cm 2 ). Accordingly, a pressurizing device which can control a pressure in proportion to a number of spray nozzles so that the effect can be exhibited sufficiently is required.
  • the most preferred pressure is 0.3 to 10 kg/cm 2 , and if the pressure is less than 0.3 kg/cm 2 , the effect cannot be obtained, and on the other hand, if the pressure is too high, a light-sensitive material is damaged or broken in some cases.
  • the air bubbling processing method is a method in which a sparger is provided at the bottom of a lower conveying roller of a processing solution tank, air or inert gas is charged into the sparger, a light-sensitive material is vibrated by air bubbles discharged from its opening, and further, a processing solution is brought in contact effectively with a front surface, a back surface and a side surface of a light-sensitive material.
  • the sparger materials having a resistance to corrosion such as rigid vinyl chloride, a stainless steel coated with polyethylene and a sintered metal are suitable, and perforation is carried out to obtain such a perforated diameter that air bubbles discharged have a size of 2 mm to 30 mm, preferably 5 mm to 15 mm, whereby a better effect can be obtained.
  • an air compressor for example, Babycon (0.4 KW, BU7TL) (trade name) manufactured by Hitachi Ltd.
  • an air pump for example, an air pump (Model Ap220, trade name) manufactured by Iwaki K.K.
  • the amount of air is required to be 2 t/min to 30 t/min, preferably 5 R/min to 20 Umin per conveying rack of an automatic processor, whereby more preferred results can be obtained.
  • the amount of air or inert gas should be controlled, but air or inert gas is preferably charged in such an amount that a vibration width of a light-sensitive material caused by air bubbles becomes 0.2 mm to 20 mm.
  • the ultrasonic oscillation processing method is a method in which an ultrasonic oscillation device is provided in a space at a bottom portion or a side wall within a processing solution tank of an automatic processor, and ultrasonic waves are irradiated to a light-sensitive material to enhance development accelerating efficiency.
  • the ultrasonic oscillation device there may be used, for example, a magnetostrictive type nickel oscillator (horn type) and a magnetostrictive type barium titanate oscillator (holder type) manufactured by Choonpa Kogyo K.K.
  • a frequency of an oscillator of the ultrasonic oscillation device to be used is preferably 5 to 1,000 KHz, particularly preferably 10 to 50 KHz in the points of the effect of the present invention and damage to machine parts of an automatic processor.
  • an irradiation method of ultrasonic waves to a light-sensitive material there may be included a method in which ultrasonic waves are irradiated directly or indirectly through a reflecting plate to a light-sensitive material. However, since ultrasonic waves are damped in proportion to an irradiating distance, a direct irradiation is more preferred.
  • the irradiation time may be at least 1 second. When a partial irradiation is effected, it may be effected at any of a primary stage, an intermediate stage or a latter stage of processing steps.
  • the vibration processing method is a method in which a light-sensitive material is vibrated between an upper roller and a lower roller in a processing solution tank of an automatic processor to carry out immersion processing effectively.
  • a vibrator which is a vibration source
  • the vibrator is fixed to the upper portion of a immersion processing tank of an automatic processor and set so that the vibrator strikes against the back side of a light-sensitive material.
  • the vibration number of the vibrator is preferably 100 to 10,000 times/min, most preferably in the range of 500 to 6,000 times/min.
  • a vibrational amplitude of a light-sensitive material to be processed is 0.2 mm to 30 mm, preferably 1 mm to 20 mm. If the amplitude is lower than 0.2 mm, no effect can be exhibited, and on the other hand, if it is too great, a light-sensitive material may be damaged in some cases.
  • the number of vibrators to be set may be different depending on a size of an automatic processor. When a processing tank comprises a plural number of tanks, at least one vibrator is set per one processing tank for obtaining preferred effect.
  • the processing time of a light-sensitive silver halide color photographic material by using a color developing solution is preferably 210 seconds or shorter and 10 seconds or longer.
  • the color developing solution is a color developing solution containing an aromatic primary amine type color developing agent preferably in an amount of 5.0 x 10- 3 mole or more, more preferably 1.0 x 10- 2 mole or more, particularly preferably 1.2 x 10- 2 to 2 x 10- 1 mole per liter of the processing solution.
  • the color developing agent of the color developing solution which can be preferably used in the present invention is described below.
  • the aromatic primary amine type color developing agent used in the preferred color developing solution as described above may include those known to the art which have been used widely in various color photographic processings. These developing agents may include aminophenol type and p-phenylenediamine type derivatives. These compounds are generally used in the form of a salt, for example, in the form of a chloride or a sulfate since they are stabler than those under a free state.
  • aminophenol type developing agent there may be mentioned, for example, o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene and 2-oxy-3-amino-1,4-dimethyl-benzene.
  • the aromatic primary amine color developing agent particularly useful in the present invention is an aromatic primary amine color developing agent having an amino group containing at least one water-soluble group, particularly preferably a compound represented by the following formula (E).
  • R 1 represents a hydrogen atom, a halogen atom or an alkyl group, and said alkyl group represents a straight or branched alkyl group having 1 to 5 carbon atoms, which may have a substituent group.
  • R 2 and R 3 each represent a hydrogen atom, or an alkyl group or an aryl group, and these groups may have a substituent group. At least one of R 2 and R 3 is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group and a sulfonamide group, or The alkyl group may further have a substituent group.
  • R 4 represents a hydrogen atom or an alkyl group, the alkyl group represents a straight or branched alkyl group having 1 to 5 carbon atoms, and p and q each represent an integer of 1 to 5.
  • p-phenylenediamine derivatives represented by the formula (E) can be used as a salt of an organic acid or an inorganic acid, and, for example, hydrochlorides, sulfates, phosphates, p-toluenesulfonates, sulfites, oxalates and benzenedisulfonates can be used.
  • E-1 and E-2 are used most preferably for exhibiting the effect of the present invention remarkably.
  • the sulfites may include sodium sulfite, sodium hydrogen sulfite, potassium sulfite and potassium hydrogen sulfite.
  • the sulfite is used in an amount of 1.0 x 10- 2 mole/t or less, preferably 5.0 x 10- 3 mole/t or less, particularly preferably 0.
  • the sulfite may be used preferably in an amount in the range of 0.1 to 40 g/t, more preferably in the range of 0.5 to 10 g/t.
  • preservative other than the sulfites there may be preferably used, as organic preservatives, hydroxylamine, hydroxylamine derivatives disclosed in Japanese Unexamined Patent Publications No. 146043/1988, No. 146042/1988, No. 146041/1988, No. 146040/1988, No. 135938/1988 and No.
  • organic preservatives other than hydroxylamine particularly hydroxylamine derivatives substituted with alkyl and hydrazines are preferably used.
  • halides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide and further organic inhibitors.
  • Their amounts to be added are preferably in the range of 0.005 to 30 g/t, more preferably in the range of 0.01 to 20 g/t.
  • organic inhibitor preferably used when the present invention is practiced, there may be mentioned nitrogen-containing heterocyclic compounds, compounds containing a mercapto group, aromatic compounds, onium compounds and compounds having an iodine atom as a substituent group, and specific examples of them are the following exemplary compounds.
  • the compound represented by the following formula (R-I) is more preferably a compound represented by the formula (R-IV) or (R-V), most preferably compounds represented by the formulae (R-VI) to (R-XI).
  • the compound represented by the following formula (R-II) is most preferably a compound represented by the formula (R-XII) or (R-XIII).
  • X and X 1 each represent a halogen atom, a mercapto group, an oxycarbonyl group, an alkyl group, an aryl group, an amino group, a hydroxyl group, a nitro group, a carboxyl group and a sulfo group
  • X 2 represents a hydrogen atom, an alkyl group, an aryl group or a double bond for forming a ring
  • Z is an atomic group necessary for forming a ring comprising a carbon atom, a nitrogen atom and a sulfur atom
  • n and m each represent 0, 1 or 2; and when n and m are 2, each X and X 1 may be the same or different.
  • Y, Yi, Y 2 and Y 3 each represent a hydrogen atom, a halogen atom, an alkyl group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, an oxycarbonyl group, a sulfo group and a sulfonyl group.
  • T represents a nitrogen atom or a phosphor atom
  • X 2 and X 3 each represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom
  • Y 4 and Ys each represent an alkyl group or an aryl group
  • Y 4 and Ys may be closed to form a hetero ring.
  • R, Ri, R 2 , Y 1 and Y 2 have the same meanings of Y, Yi, Y 2 and Y 3 in the description of the above formula (R-II), respectively.
  • m and n have the same meanings of those in the formula (R-I).
  • the organic inhibitor in the present invention has been described above, and further specific examples thereof may include (Z-1) to (Z-3), (Z-6), (Z-8), (Z-13), (Z-15) to (Z-17), (Z-19), (Z-22) to (Z-25), (Z-29), (Z-31) to (Z-38), (Z-40), (Z-41), (Z-43) to (Z-64) and (Z-66) to (Z-73) described on pp. 101 to 113 of Japanese Unexamined Patent Publication No. 170955/1987.
  • alkali agents such as sodium hydroxide and sodium carbonate, alkali metal thiocyanate, alkali metal halides, benzyl alcohol, a water softener, a thickener and a developing accelerator can be further contained as desired.
  • additives added in the above color developing solution may include an antistaining agent, an antisludging agent, a preservative, an interlayer effect accelerator and a chelating agent.
  • the color developing solution of the present invention is used preferably at a pH of 9 or more, particularly preferably at a pH of 9 to 13.
  • the color developing solution is employed preferably at a temperature of 30 °C or higher, particularly preferably in the range of 33 °C to 60 C.
  • the stabilizing solution to be used in the present invention can be applied to a stabilizing solution used in a stabilizing processing which is the final processing step of a light-sensitive silver halide color photographic material. Further, the present invention can be also applied to the case where a light-sensitive silver halide color photographic material is processed by a processing solution having fixing ability, for example, a fixing solution or a bleach-fixing solution, followed by stabilizing processing substantially without washing.
  • the light-sensitive silver halide color photographic material to be processed is not particularly limited and may include negative films, printing papers and color copies, and can be processed by using the stabilizing solution of the present invention.
  • the replenishing amount of the stabilizing solution of the present invention is preferably 1- to 80-fold of the amount brought in from the previous bath per unit area of a color photographic material to be processed, but in the present invention, a stabilizing processing tank is preferably constituted so that the concentration of the components of the previous bath (the bleach-fixing solution or the fixing solution) in the stabilizing solution becomes 1/100 or less, preferably 1/100 to 1/100000, more preferably 1/200 to 1/50000 in the ultimate stabilizing solution tank in the points of low pollution and solution storability.
  • the stabilizing processing tank may be constituted of plural tanks, and said plural tanks are preferably 2 tanks to 6 tanks in the present invention.
  • a countercurrent system (a system in which a solution is supplied to a latter bath and then a solution is overflown from a previous bath) is employed particularly preferably in the point of the effect of the present invention, particularly in the points of low pollution and improvement of image storage.
  • the amount to be brought in varies depending on a kind of a light-sensitive material, conveying speed and a conveying system of an automatic processor, and a squeeze system of a light-sensitive material surface, but in the case of a light-sensitive color material, the amount to be brought in is generally 50 ml/m 2 to 150 ml/m 2 .
  • the replenishing amount which can exhibit the effect of the present invention more markedly relative to said amount to be brought in is in the range of 50 ml/m 2 to 4.0 l/m 2 , particularly in the range of 100 ml/m 2 to 1,500 ml/m 2 .
  • the processing with the stabilizing solution is carried out at a processing temperature of 15 to 60 C, preferably in the range of 20 to 45 C.
  • chelating agents represented by the following formulae (CH-I) to (CH-III) are preferably contained.
  • E represents an alkylene group, a cycloalkylene group, a phenylene group, -R 5 '-O-R 5 '-, -Rs'-O-Rs'-O-Rs'-or -Rs'-Z-Rs'- where Z represents R l ' to R 6 ' each represent an alkylene group;
  • R 7 ' represents an alkyl group, an aryl group or a nitrogen-containing 6-membered cyclic group
  • M represents a hydrogen atom or an alkali metal atom.
  • R 8 ', R s ' and Rio' each represent a hydrogen atom, a hydroxyl group, -COOM, -P0 3 M 2 or an alkyl group
  • B 1 , B 2 and B 3 each represent a hydrogen atom, a hydroxyl group, -COOM, -P0 3 M 2 or where J represents a hydrogen atom, an alkyl group, -C 2 H 4 0H or -P0 3 M 2 where M represents a hydrogen atom or an alkali metal atom
  • n and m each represent 0 or 1.
  • the above chelating agents preferably used in the stabilizing solution are used preferably in an amount of 0.01 to 100 g, more preferably 0.05 to 50 g, particularly preferably 0.1 to 20 g per liter of the stabilizing solution of the present invention.
  • the stabilizing solution has preferably a pH value in the range of 4.0 to 9.0, more preferably in the range of 5.5 to 9.0, particularly preferably in the range of 6.0 to 8.5.
  • any alkali agent or acidic agent generally known can be used as a pH controller which can be contained in the stabilizing solution.
  • organic acid salts salts of citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid
  • pH controllers phosphate, borate, hydrochloride and sulfate
  • surfactants phosphate, borate, hydrochloride and sulfate
  • antiseptic agents salts of metals such as Bi, Mg, Zn, Ni, Al, Sn, Ti and Zr
  • Ca and Mg ions may be contained in an amount of 5 ppm or less in the stabilizing solution.
  • an antifungal agent preferably used in the stabilizing solution to be used in the present invention there may be included hydroxybenzoate compounds, phenol type compounds, thiazole type compounds, pyridine type compounds, guanidine type compounds, carbamate type compounds, morpholine type compounds, phosphonium type compounds, quaternary ammonium type compounds, urea type compounds, isoxazole type compounds, propanolamine type compounds, sulfamide type compounds, amino acid type compounds and benztriazole type compounds.
  • phenol type compounds, thiazole type compounds and benztriazole type compounds are particularly preferred.
  • the amount of the antifungal agents to be added in the stabilizing solution are preferably in the range of 0.001 to 20 g, particularly preferably in the range of 0.005 to 10 g per liter of the stabilizing solution.
  • the stabilizing solution of the present invention for the purpose of stabilizing dyes, formalin, hexamethylenetetramine, triazine type compounds, N-methylol compounds (dimethylolurea, trimethylolurea, dimethylolguanidine, N-hyroxymethylhydroxyethylamine and trimethylolmelamine) and aliphatic aldehyde can be used in combination.
  • the amount of formalin is preferably made 0, which is a preferred embodiment also from the point of solution storability.
  • sulfite ion-releasing compounds and at least one of compounds represented by the following formulae (SA) and (SB) are preferably contained, whereby solution storability can be further improved without exerting any bad influence on photographic performances.
  • A,, A 2 , A3 and A4 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group.
  • M represents an alkali metal atom (Na, K and Li).
  • n represents an integer of 1 to 5.
  • the alkyl group having 1 to 6 carbon atoms may include those which are straight or branched, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an iso-pentyl group, an n-hexyl group and an isohexyl group, which may be substituted.
  • substituent group there may be mentioned specifically a formyl group (e.g. each group of formylmethyl and 2-formylethyl), an amino group (e.g. each group of aminomethyl and aminoethyl), a hydroxyl group (e.g.
  • each group of hydroxymethyl, 2-hydroxyethyl and 2-hydroxypropyl an alkoxy group (e.g. each group of methoxy and ethoxy) and a halogen atom (e.g. each group of chloromethyl, trichloromethyl and dibromomethyl).
  • the alkenyl group may be substituted or unsubstituted.
  • the unsubstituted alkenyl group may include each group of vinyl and 2-propenyl, and the substituted one may include, for example, each group of 1,2-dichloro-2-carboxyvinyl and 2-phenylvinyl.
  • the compounds represented by the above formulae (SA) and (SB) may be used singly or in combination.
  • the amount to be added is preferably 0.1 to 50 g, more preferably 0.1 to 20 g per liter of the stabilizing solution of the present invention.
  • the sulfite ion-releasing compound to be used in the present invention may be either an organic compound or an inorganic compound as long as it releases a sulfite ion, but preferably an inorganic salt.
  • Preferred specific examples may include:
  • the amount of the above sulfite ion-releasing compound to be added in a washing-substituting stabilizing solution, a stabilizing solution and a processing solution by which a washing-substituting stabilizing processing and a stabilizing processing can be carried out at the same time is preferably 0.01 to 0.1 mole/t, more preferably 0.02 to 0.1 mole/l.
  • surfactants represented by the following formulae (I) and (III), triethanolamine and polyvinyl pyrrolidones are preferably contained.
  • R 1 represents a monovalent organic group
  • R 2 represents an ethylene group or a propylene group
  • m represents an integer of 4 to 50
  • X 1 represents a hydrogen atom, -S0 3 M or -PO3M2 where M represents a hydrogen atom, an alkali metal atom or -NH 4 .
  • Specific exemplary compounds may include:
  • the compounds represented by the above formula (I) can be used in an amount in the range of 0.1 to 40 g, preferably in the range of 0.3 to 20 g per liter of the stabilizing solution of the present invention.
  • the polyvinyl pyrrolidones to be used in the present invention may preferably have an average molecular weight of 1,000 to 70,000, and their representative specific examples may include the following compounds.
  • the polymers or copolymers of the present invention can be obtained easily since a part of them are commercially available as described above, and can be synthesized easily according to the method described in "Preparative Methods of Polymer Chemistry” written by W.R. Sorenson and T.W. Campbell published by John Wilery and Sons, Inc. in 1961.
  • the polymers or copolymers of the present invention may be used singly or in combination of two or more kinds, and their amount to be used are in the range of 0.01 g to 100 g, preferably in the range of 0.05 g to 10 g per liter of the image stabilizing solution.
  • the polymers or copolymers of the present invention may be added in the stabilizing solution, or may be added in a replenishing solution and then replenished in the stabilizing solution, and also these two embodiments may be used in combination.
  • R s represents a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group
  • Rio, R 11 and R 12 each represent a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl and propyl) and the above R i o, R 11 and R 12 may be the same or different, respectively
  • l 1 to l 3 each represent an integer of 0 or 1 to 4
  • p, q 1 and q 2 each represent an integer of 1 to 15.
  • the amount is less than 0.01 g, stain on a light-sensitive material surface becomes conspicuous, and if the amount is more than 20 g, a large amount of the organic siloxane type compound is attached to a light-sensitive material surface, whereby the surface is stained.
  • the water-soluble organic siloxane type compounds of the present invention are common water-soluble organic siloxane type compounds as disclosed in Japanese Unexamined Patent Publication No. 18333/1972, Japanese Patent Publication No. 51172/1980, Japanese Patent Publication No. 37538/1976, Japanese Unexamined Patent Publication No. 62128/1974 and U.S. Patent No. 3,545,970.
  • the light-sensitive material according to the present invention may be either of a coupler-in-emulsion type development system in which a coupler is contained in a light-sensitive material (see U.S. Patents No. 2,376,679 and No. 2,801,171) or of a coupler-in-developer type development system in which a coupler is contained in a developing solution (see U.S. Patents No. 2,252,718, No. 2,592,243 and No. 2,590,970).
  • a coupler any coupler generally known in the art can be used.
  • cyan couplers outside the scope of the present invention may be used in combination, and said cyan couplers used in combination may include those which are based on a naphthol or phenol structure and form an indoaniline dye by coupling.
  • magenta coupler there may be used magenta couplers having a 5-pyrazolone ring having an active methylene group as a skeletal structure and pyrazoloazole type magenta couplers.
  • yellow coupler there may be used yellow couplers having an active methylene group and having a benzoylacetanilide, pivalylacetanilide or acylacetanilide structure, which may have a substituent group or no substituent group at a coupling position.
  • the preferred cyan coupler may include those represented by the following formulae (C-A), (C-B) and (C-C).
  • R 1 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • Y represents a group represented by -CONHCOR 2 or -CONHS0 2 R 2 (where R 2 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • R 3 represents a hydrogen atom or a group represented by R 2 ; and R 2 and R 3 may be the same or different and may be bonded to each other to form a 5- or 6-membered hetero ring)
  • Z represents a hydrogen atom or a group which can be eliminated by coupling reaction with an oxidized product of an aromatic primary amine type color developing agent.
  • R 11 represents -CONR 14 R 15 , -NHCOR 14 , -NHCOOR 16 , -NHSO 2 R 16 , -NHCONR 14 R 15 or -NHSO 2 NR 14 R 15 ;
  • R 12 represents a monovalent group;
  • R 13 represents a substituent group;
  • X represents a hydrogen atom or a group which can be eliminated by coupling reaction with an oxidized product of an aromatic primary amine type color developing agent;
  • l represents 0 or 1;
  • m represents 0 to 3;
  • R 14 and R 15 each represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group;
  • R 16 represents an aromatic group, an aliphatic group or a heterocyclic group; when m is 2 or 3, the respective R 13 's may be the same or different and may be bonded to each other to form a ring;
  • Ru and R15, R 12 and R 13 , and R 12 and X may be bonded
  • Y is a group represented -CONHCOR 2 or -CONHS0 2 R 2 .
  • R, and R 2 each represent an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (e.g. each group of methyl, ethyl, t-butyl and dodecyl), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (an allyl group and a heptadecenyl group), a cycloalkyl group, preferably 5- to 7-membered cyclic groups (e.g.
  • R 3 represents a hydrogen atom or a group represented by R 2 .
  • R 2 and R 3 may be bonded to each other to form a 5- or 6-membered hetero ring.
  • any desired substituent group can be introduced, and may include, for example, an alkyl group having 1 to 10 carbon atoms (e.g. methyl, i-propyl, i-butyl, t-butyl and t-octyl), an aryl group (e.g. phenyl and naphthyl), a halogen atom (fluorine, chlorine and bromine), a cyano group, a nitro group, a sulfonamide group (e.g.
  • R 1 represents a ballast group necessary for imparting diffusion-proof property to the cyan couplers represented by the formula (C-A) and the formula (C-B) and cyan dyes formed from said cyan couplers.
  • R 1 may be preferably an alkyl group having 4 to 30 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group, and, for example, a straight or branched alkyl group (e.g. t-butyl, n-octyl, t-octyl and n-dodecyl) and a 5- or 6-membered heterocyclic group.
  • Z represents a hydrogen atom or a group which can be eliminated by coupling reaction with an oxidized product of a color developing agent.
  • Z may include, for example, a halogen atom (e.g.
  • the cyan coupler represented by the formula (C-D) is preferred.
  • R 4 is a substituted or unsubstituted aryl group (particularly preferably a phenyl group).
  • the substituent group may include at least one substituted group selected from S0 2 Rs, a halogen atom (fluorine, chlorine and bromine), -CF 3 , -N0 2 , -CN, -CORs, -COORs, -S0 2 0Rs, and
  • R 5 represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (e.g. each group of methyl, ethyl, t-butyl and dodecyl), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (an allyl group and a heptadecenyl group), a cycloalkyl group, preferably 5- to 7-membered cyclic groups (e.g. cyclohexyl) and an aryl group (e.g. a phenyl group, a tolyl group and a naphthyl group), and R 6 is a hydrogen atom or a group represented by R s .
  • R s represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (e.g. each group of methyl, ethyl, t-butyl and dodecyl), an alkenyl group, preferably
  • a suitable compound of the cyan coupler of the present invention represented by the formula (C-D) is a compound in which R 4 is a substituted or unsubstituted phenyl group, and a substituent group of the phenyl group is cyano group, nitro group, -S0 2 R 7 (where R 7 is an alkyl group), a halogen atom or trifluoromethyl group.
  • Z and R 1 each have the same meanings of those in the formulae (C-A) and (C-B).
  • a preferred example of the ballast group represented by R 1 is a group represented by the following formula (C-E). wherein J represents an oxygen atom, a sulfur atom or a sulfonyl group; K represents an integer of 0 to 4; l represents 0 or 1; when K is 2 or more, two or more Rg's may be the same or different; R 8 represents a straight or branched substituted alkylene group having 1 to 20 carbon atoms such as an aryl group; R 9 represents a monovalent group, preferably a hydrogen atom, a halogen atom (e.g.
  • an alkyl group preferably a straight or branched alkyl group having 1 to 20 carbon atoms (e.g. each group of methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl and phenethyl), an aryl group (e.g. a phenyl group), a heterocyclic group (e.g. a nitrogen-containing heterocyclic group), an alkoxy group, preferably a straight or branched alkoxy group having 1 to 20 carbon atoms (e.g.
  • an acetoxy group and a benzoyloxy group a carboxy group, an alkyloxycarbonyl group, preferably a straight or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably a phenoxycarbonyl group, an alkylthio group, preferably an acyl group having 1 to 20 carbon atoms, preferably a straight or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably a straight or branched alkylcarboamide group having 1 to 20 carbon atoms, a benzenecarboamide group, a sulfonamide group, preferably a straight or branched alkylsulfonamide group or benzenesulfonamide group having 1 to 20 carbon atoms, a carbamoyl group, preferably a straight or branched alkylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon
  • Each group represented by R 12 to R 17 in the formula (C-C) may include those having a substituent group.
  • R 16 an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms and a heterocyclic group having 1 to 30 carbon atoms are preferred, and as R 14 and R 15 , a hydrogen atom and those mentioned as a preferred example of R 16 are preferred.
  • R 12 preferred are a hydrogen atom which bonded directly or through NH, CO or S0 2 to NH, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms, -OR 18 , -COR 18 , -PO( ⁇ OR 20 ) 2 , -PO(R 20 ) 2 , -C0 2 R 20 , -S0 2 R 20 or -S0 2 0R 20 (where R 18 , R 19 and R 20 each have the same meanings of R 14 , R 15 and R 16 defined above; R 18 and R 19 may be bonded to form a ring).
  • R 17 is preferably an aromatic group having 6 to 30 carbon atoms, and as a representative example of a substituent group of R 17 , there may be mentioned a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an ureido group, an acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, an imide group, an aliphatic group and an aliphatic oxycarbonyl group.
  • R 17
  • R 13 there may be mentioned a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an ureido group, an acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group and an imide group, and a number of carbon atoms contained in this R 13 is preferably 0 to 13.
  • m 2
  • an example of a cyclic R 13 is a dioxymethylene group.
  • R 11 is particularly preferably -CONR 14 R 15
  • m is preferably
  • R 12 is preferably -COR 18 , -COOR 20 , -S0 2 R 20 , -CONR 18 R 19 and -SO 2 NR 18 R 19 which are bonded directly to NH, more preferably -COOR 20 , -COR 18 and -S0 2 R 20 which are bonded directly to NH, and among them most preferably -COOR 20 .
  • Coupler represented by the formula (C-C) are disclosed in Japanese Unexamined Patent Publications No. 237448/1985, No. 153640/1986, No. 145557/1986, No. 85242/1987, No. 15529/1973, No. 117422/1975, No. 18315/1977, No. 90932/1977, No. 52423/1978, No. 48237/1979, No. 66129/1979, No. 32071/1980, No. 65957/1980, No. 105226/1980, No. 1938/1981, No. 12643/1981, No. 27147/1981, No. 126832/1981 and No. 95346/1983, and U.S. Patent No. 3,488,193, and can be synthesized according to the methods disclosed in these publications.
  • the coupler For adding the coupler to a light-sensitive material, depending on physical properties (e.g. solubility) of the coupler, various methods such as the oil-in-water type emulsifying dispersion method in which a water-insoluble high boiling point organic solvent is used, the alkali dispersion method in which a coupler is added.in the form of an alkaline solution, the latex dispersion method and the solid dispersion method in which a coupler is added directly in the form of minute solid can be employed.
  • various methods such as the oil-in-water type emulsifying dispersion method in which a water-insoluble high boiling point organic solvent is used, the alkali dispersion method in which a coupler is added.in the form of an alkaline solution, the latex dispersion method and the solid dispersion method in which a coupler is added directly in the form of minute solid can be employed.
  • the amount of the coupler to be added is generally 1.0 x 10- 3 mole to 1.0 mole, preferably in the range of 5.0 x 10- 3 mole to 8.0 x 10 -1 mole per mole of silver halide.
  • the preferred cyan coupler may include those represented by the following formula (C-1). wherein R 1 represents a ballast group; H 2 represents an alkyl group having or more carbon atoms; ana Z 1 represents a hydrogen atom, or an atom or a group which can be eliminated by the reaction with an oxidized product of a color developing agent.
  • the alkyl group represented by R 2 may be straight or branched and include those having a substituent group.
  • R 2 is preferably an alkyl group having 2 to 6 carbon atoms.
  • the ballast group represented by R 1 is an organic group having a size and a shape which can give a volume sufficient to substantially prevent diffusion of a coupler from a layer in which the coupler is used to other layers, to a coupler molecule.
  • ballast group is represented by the following formula. wherein R B1 represents an alkyl group having 1 to 12 carbon atoms; Ar represents an aryl group such as a phenyl group; and the aryl group includes those having a substituent groups.
  • the cyan dye-forming coupler represented by the above formula (C-1) of the present invention can be used generally in an amount of 1 x 10- 3 mole to 1 mole, preferably in the range of 1 x 10- 2 mole to 8 x 10- 1 mole per mole of silver halide.
  • the cyan coupler represented by the formula (C-1) is preferably used in combination with a 2,5-diacylaminophenol type cyan coupler.
  • a coupler represented by the following formula (C-2) is preferred.
  • R 1 represents an alkyl group or an aryl group
  • R 2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • R 3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group
  • R 3 may form a ring together with Ri
  • Z represents a hydrogen atom, or an atom or a group which can be eliminated by reaction with an oxidized product of an aromatic primary amine type color developing agent.
  • the alkyl group represented by R 1 is preferably alkyl groups having 1 to 32 carbon atoms, and these alkyl groups may be straight or branched and also include those having a substituent group.
  • the aryl group represented by R 1 is preferably a phenyl group, and also includes those having a substituent group.
  • the alkyl group represented by R 2 is preferably alkyl groups having 1 to 32 carbon atoms, and these alkyl groups may be straight or branched and also include those having a substituent group.
  • the cycloalkyl group represented by R 2 is preferably alkyl groups having 3 to 12 carbon atoms, and these cycloalkyl groups also include those having a substituent group.
  • the aryl group represented by R 2 is preferably a phenyl group, and also includes those having a substituent group.
  • the heterocyclic group represented by R 2 is preferably 5- to 7-membered heterocyclic groups, and these heterocyclic groups include those having a substituent group and may be fused.
  • R 3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and said alkyl group and said alkoxy group may include those having a substituent group. However, R 3 is preferably a hydrogen atom.
  • the ring formed by R 1 and R 3 is preferably a 5- or 6-membered ring, and an example thereof may include
  • an atom or a group represented by Z which can be eliminated by reaction with an oxidized product of a color developing agent may include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group and an imide group (including those having a substituent group), but preferably a halogen atom, an aryloxy group and an alkoxy group.
  • cyan couplers particularly preferred are a cyan coupler represented by the following formula (C-2A).
  • R G1 represent a phenyl group substituted with at least one halogen atom and further includes those having a substituent group other than a halogen atom
  • R G2 has the same meaning of R 1 in the above formula (C-2)
  • Z G represents a halogen atom, an aryloxy group or an alkoxy group and includes those having a substituent group.
  • cyan coupler there may be further included, for example, 2,5- diacylamino type cyan couplers disclosed on pp. 26 to 35 of Japanese Unexamined Patent Publication No. 178962/1987, in the left lower column on p. 7 to the right lower column on p. 10 of Japanese Unexamined Patent Publication No. 225155/1985, in the left upper column on p. 6 to the right lower column on p. 8 of Japanese Unexamined Patent Publication No. 222853/1985 and in the left lower column on p. 6 to the left upper column on p. 9 of Japanese Unexamined Patent Publication No. 185335/1984, and these couplers can be synthesized according to the methods disclosed in these publications.
  • the cyan dye-forming coupler represented by the above formula (C-2) of the present invention can be used generally in an amount of 1 x 10- 3 to 1 mole, preferably in the range of 1 x 10- 2 mole to 8 x 10- 1 mole per mole of silver halide.
  • magenta coupler preferably used in the present invention is represented by the following formula (M-1).
  • Z m represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by said Z m may have a substituent group.
  • X m represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized product of a color developing agent.
  • the substituent group represented by R m is not particularly limited, but may representatively include each group of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkenyl.
  • a halogen atom and each group of cycloalkenyl, alkynyl, hetero ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclic thio, and also a spiro-compound residue and a bridged hydrocarbon compound residue.
  • the alkyl group represented by R m are preferably alkyl groups having 1 to 32 carbon atoms, which may be straight or branched.
  • the aryl group represented by R m is preferably a phenyl group.
  • the acylamino group represented by R m may include an alkylcarbonylamino group and an arylcarbonylamino group.
  • the sulfonamide group represented by R m may include, for example, an alkylsulfonylamino group and an arylsulfonylamino group.
  • the alkyl component and aryl component in the alkylthio group and arylthio group represented by R m are each the alkyl group and aryl group represented by the above R m .
  • the alkenyl group represented by R m is alkenyl groups having 2 to 32 carbon atoms, and the cycloalkyl group is cycloalkyl groups preferably having 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.
  • the alkenyl groups may be straight or branched.
  • the cycloalkenyl group represented by R m is cycloalkenyl groups preferably having 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.
  • the sulfonyl group represented by R m may include an alkylsulfonyl group and an arylsulfonyl group; the sulfinyl group, for example, an alkylsulfinyl group and arylsulfinyl group; the phosphonyl group, for example, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group and an arylphosphonyl group; the acyl group, for example, an alkylcarbonyl group and an arylcarbonyl group; the carbamoyl group, for example, an alkylcarbamoyl group and an arylcarbamoyl group; the sulfamoyl group, for example, an alkylsulfamoyl group and an arylsulfamoyl group; the acyloxy group, for example, an alkylcarbonyloxy group and an aryl
  • the group represented by X m which can be eliminated by reaction with an oxidized product of a color developing agent, may include, for example, a halogen atom (a chlorine atom, a bromine atom and a fluorine atom), and each group of alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxycarbonylthio, acylamino, sulfonamide, nitrogen-containing hetero ring which is bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and wherein R m1' has the same meaning as the above R m ; Z' has the same meaning as the above Z; and R m2' and R m3' each group
  • the nitrogen-containing hetero ring formed by Z m or Z' may include, for example, a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring, and as a substituent group which may be possessed by the above rings, there may be mentioned those in the description of the above R m .
  • R m1 to R m8 and X m each have the same meaning as the above R m and Xm.
  • magenta couplers represented by the formula (M-I) preferred is a magenta coupler represented by the following formula (M-VIII). wherein R m1 , X m and Z m1 each have the same meanings as R m1 , X m and Z m in the formula (M-I).
  • magenta couplers represented by the above formulae (M-II) to (M-VII) particularly preferred is the magenta coupler represented by the formula (M-II).
  • the substituent groups which may be possessed by the ring formed by Z m in the formula (M-I) and the ring formed by Z m1 in the formula (M-VIII), and R m2 to R m8 in the formulae (M-II) to (M-VI) are preferably those represented by the following formula (M-IX). wherein R m1 represents an alkylene group; and R m2 represents an alkyl group, a cycloalkyl group or an aryl group.
  • the alkylene group represented by the above R m1 may have preferably 2 or more, more preferably 3 to 6 carbon atoms in its straight portion, and may be either straight or branched.
  • the cycloalkyl group represented by the above R m2 is preferably 5- or 6-membered.
  • R m and R m1 on the above hetero ring are represented by the following formula (M-X). wherein R m g, R m10 and R m11 each have the same meaning of the above R m .
  • R m9 and R m10 may be bonded to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene and hetero ring), and further, R m11 may be bonded to said ring to constitute a bridged hydrocarbon compound residue.
  • a saturated or unsaturated ring e.g. cycloalkane, cycloalkene and hetero ring
  • R m9 to R m11 are alkyl groups
  • R m9 to R m11 are a hydrogen atom
  • R m9 and R m10 are bonded to form cycloalkyl together with a root carbon atom
  • R m9 to R m11 are alkyl groups, and the other one is a hydrogen atom or an alkyl group.
  • R m and R m1 on the above hetero rina are represented bv the followina formula (M-XI). wherein Rm12 has the same meaning of the above R m .
  • R m12 is preferably a hydrogen atom or an alkyl group.
  • the above couplers can be synthesized by referring to Journal of the Chemical Society, Perkin I (1977), pp. 2047 to 2052, U.S. Patent No. 3,725,067, and Japanese Unexamined Patent Publications No. 99437/1984, No. 42045/1984, No. 162548/1984, No. 171956/1984, No. 33552/1985, No. 43659/1985, No. 172982/1985 and No. 43659/1985.
  • the magenta coupler represented by the formula (M-I) is used generally in an amount of 1 x 10- 3 mole to 1 mole, preferably in the range of 1 x 10- 2 mole to 8 x 10- 8 mole per mole of silver halide.
  • coupler represented by the formula (M-I) can be used in combination with other kinds of magenta dye-forming couplers.
  • a polymer coupler In the present invention, it is also a preferred embodiment to use a polymer coupler.
  • a polymer coupler As the polymer coupler, P-2, P-5, P-13, P-14, P-17, P-22 and P-23 disclosed in Japanese Unexamined Patent Publication No. 239748/1985 are preferably used, and further, the following polymer couplers are useful for exhibiting the effect of the present invention.
  • a preferred yellow coupler is a benzoylacetanilide type yellow coupler.
  • the benzoylacetalinide type yellow coupler may include any benzoylacetanilide derivative, but preferred is a compound represented by the following formula (YB-I). wherein R 1 to R 7 and X each represent a hydrogen atom or a substituent group; and R i , R 2 , and R 3 may be preferably either the same or different, and each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group, a carbamoyl group, an alkoxycarbonyl group, a sulfonamide group or a sulfamoyl group.
  • R 1 to R 7 and X each represent a hydrogen atom or a substituent group
  • R i , R 2 , and R 3 may be preferably either the same or different, and each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
  • R 4 , Rs, R 6 and R 7 may be the same or different, and preferably, each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group or a sulfonamide group.
  • W represents preferably a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or a dialkylamino group.
  • X 1 represents a hydrogen atom or an eliminatable group.
  • the eliminatable group there may be mentioned, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group and a saturated or unsaturated 5-membered or 6- membered nitrogen-containing heterocyclic group, and particularly preferred groups are represented by the formulae (YB-II) and (YB-III).
  • Y 1 represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring, and the group of non-metallic atoms may include those having a substituent group.
  • Ar represents an aryl group, and said aryl group may include those having a substituent group.
  • benzoylacetanilide type yellow couplers may include those disclosed in U.S. Patents No. 2,875,057, No. 3,725,072 and No. 3,891,445, Japanese Patent Publication No. 10783/1976, and Japanese Unexamined Patent Publications No. 73147/1973, No. 6341/1975, No. 102636/1976, No. 115219/1977, No. 21448/1979, No. 95237/1981, No. 159163/1984, No. 174838/1984, No. 206835/1984, No. 187560/1989, No. 207748/1989, No. 207749/1989, No. 214848/1989, No. 227152/1989, No. 231050/1989, No. 295256/1989, No. 309057/1989, No. 341240/1989, No. 316744/1989 and No. 316745/1989, and they can be synthesized according to the methods disclosed in the publications.
  • Two or more of the benzoylacetanilide type yellow couplers according to the present invention may be used, and yellow couplers other than these couplers may be used in combination.
  • the yellow coupler For adding the yellow coupler to a light-sensitive material, depending on physical properties (e.g. solubility) of said yellow coupler, various methods such as the oil-in-water type emulsifying dispersion method in which a water-insoluble high boiling point organic solvent is used, the alkali dispersion method in which a coupler is added.in the form of an alkaline solution, the latex dispersion method and the solid dispersion method in which a coupler is added directly in the form of minute solid can be employed.
  • various methods such as the oil-in-water type emulsifying dispersion method in which a water-insoluble high boiling point organic solvent is used, the alkali dispersion method in which a coupler is added.in the form of an alkaline solution, the latex dispersion method and the solid dispersion method in which a coupler is added directly in the form of minute solid can be employed.
  • the total amount of the yellow coupler to be added is generally 1.0 x 10- 3 mole to 1.0 mole, preferably in the range of 5.0 x 10- 3 mole to 8.0 x 10- 1 mole per mole of silver halide.
  • the benzoylacetanilide type yellow coupler according the present invention is generally contained in a blue-sensitive silver halide emulsion layer, but, depending on a purpose, it may be also contained in a green-sensitive or red-sensitive silver halide emulsion layer having sensitivity to colors other than blue.
  • a preferred yellow coupler is represented by the following formula (Y-1). wherein R 1 represents an alkyl group or a cycloalkyl group; R 2 represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group; R 3 represents a group with which a benzene ring can be substituted; n represents 0 or 1; Y represents a monovalent ballast group; and Z represents a hydrogen atom, or an atom or a group which can be eliminated at the time of coupling.
  • the alkyl group represented by R 1 may be straight or branched, and may include, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a dodecyl group.
  • These alkyl groups may further include those having a substituent group, and as the substituent group, there may be mentioned, for example, a halogen atom and each group of aryl, alkoxy, aryloxy, alkylsulfonyl, acylamino and hydroxy.
  • the cycloalkyl group represented by R 1 may include a cyclopropyl group, a cyclohexyl group and an adamantyl group.
  • R 1 is preferably a branched alkyl group.
  • the alkyl group and the cycloalkyl group represented by R 2 there may be mentioned the same groups in the case of Ri, and as the aryl group, there may be mentioned, for example, a phenyl group.
  • These alkyl groups, cycloalkyl groups and aryl groups represented by R 2 may include those having a substituent group similarly as in the case of R 1 .
  • the acyl group there may be mentioned, for example, an acetyl group, a propionyl group, a butyryl group, a hexanoyl group and a benzoyl group.
  • R 2 is preferably an alkyl group and an aryl group, more preferably an alkyl group.
  • R 3 is not particularly limited as long as it is a group with which a benzene ring can be substituted, and may specifically include a halogen atom (e.g. a chlorine atom), an alkyl group (e.g. an ethyl group, an i-propyl group and a t-butyl group), an alkoxy group (e.g. a methoxy group), an aryloxy group (e.g. a phenyloxy group), an acyloxy group (e.g. a methylcarbonyloxy group and a benzoyloxy group), an acylamino group (e.g.
  • a halogen atom e.g. a chlorine atom
  • an alkyl group e.g. an ethyl group, an i-propyl group and a t-butyl group
  • an alkoxy group e.g. a methoxy group
  • an aryloxy group e.g
  • an acetamide group and a phenylcarbonylamino group a carbamoyl group (e.g. an N-methylcarbamoyl group and an N-phenylcarbamoyl group), an alkylsulfonamide group (e.g. an ethylsul- fonylamino group), an arylsulfonamide group (e.g. a phenylsulfonylamino group), a sulfamoyl group (e.g. an N-propylsulfamoyl group and an N-phenylsulfamoyl group) and an imide group (e.g. a succinimide group and a glutarimide group).
  • a carbamoyl group e.g. an N-methylcarbamoyl group and an N-phenylcarbamoyl group
  • an alkylsulfonamide group e.g. an e
  • Z represents a group which is eliminated at the time of coupling reaction with an oxidized product of a developing agent, and, for example, represents a group represented by the following formula (Y-2) or (Y-3).
  • R 10 represents an aryl group or a heterocyclic group including those having a substituent group.
  • Z represents a group of non-metallic atoms necessary for forming a 5- or 6- membered ring together with a nitrogen atom.
  • the yellow dye-forming coupler represented by the above formula (Y-1) of the present invention can be used generally in an amount of 1 x 10- 3 mole to 1 mole, preferably in the range of 1 x 10- 2 mole to 8 x 10 -1 mole per mole of silver halide.
  • the effect of the present invention can be exhibited more favorably.
  • BAR-A a coupler residue which can undergo coupling reaction with an oxidized product of a color developing agent
  • * represents a coupling position of the coupler
  • TIME represents a timing group, m and each represent 0 or 1
  • R 1 represents a bonding group (preferably an alkylene group having 1 to 8 carbon atoms)
  • R 2 represents a hydrogen atom, a cyano group, -COR 3 , -CSR 3 , or a hetero ring (where R 3 represents an alkyl group and an aryl group; and R 4 , R 5 and R 6 each represent a hydrogen atom, an alkyl group and an aryl group).
  • Rbi represents a divalent aliphatic group having 1 to 8 carbon atoms or (where L represents a divalent aliphatic group having 1 to 8 carbon atoms or a phenylene group), and Rb 2 represents a water-soluble group or a precursor thereof.
  • the coupler residue represented by Cp may generally include a residue which forms an yellow, magenta or cyan dye and a residue which forms a substantially colorless product.
  • coupler residue represented by Cp as a representative yellow coupler residue, there may be mentioned, for example, those disclosed in U.S. Patents No. 2,298,443, No. 2,407,210, No. 2,875,057, No. 3,048,194, No. 3,265,506 and No. 3,447,928, and Farbkupp-lereine Literaturuversiecht Agfa Mitteilung (Band II), pp. 112 to 126 (1961).
  • acylacetanilides for example, benzoylacetanilides and pivaloylacetanilides are preferred.
  • magenta coupler residue there may be mentioned, for example, those disclosed in U.S. Patents No. 2,369,489, No. 2,343,703, No. 2,311,182, No. 2,600,788, No. 2,908,573, No. 3,062,653, No. 3,152,896, No. 3,519,429, No. 3,725,067 and No. 4,540,654, Japanese Unexamined Patent Publication No. 162548/1984, and the above Agfa Mitannon (Band II), pp. 126 to 156 (1961).
  • pyrazolones or pyrazoloazoles e.g. pyrazoloimidazole and pyrazolotriazole are preferred.
  • cyan coupler residue As a representative cyan coupler residue, there may be mentioned, for example, those disclosed in U.S. Patents No. 2,367,531, No. 2,423,730, No. 2,472,293, No. 2,772,162, No. 2,395,826, No. 3,002,836, No. 3,034,892, No. 3,041,236 and No. 4,666,999, and the above Agfa Mitannon (Band II), pp 156 to 175 (1961). Among these, phenols or naphthols are preferred.
  • the timing group represented by TIME is a group which enables releasing of a bleaching accelerator group, or ( ⁇ S-Rb 1 -Rb 2 ) from Cp under time control, and in this group, a group which can control a speed of reaction between Cp and an oxidized product of a color developing agent, a diffusion speed of or -TIME-S-Rb 1 -Rb 2 released from Cp, and a releasing speed of said bleaching accelerator group may be contained.
  • a representative timing group there may be mentioned a group which releases a bleaching accelerator group by the intermolecular nucleophilic substitution reaction disclosed in U.S. Patent No. 4,248,962 and Japanese Unexamined Patent Publication No.
  • Rbi represents a divalent aliphatic group having 1 to 8 carbon atoms or (where L represents a divalent aliphatic group having 1 to 8 carbon atoms or a phenylene group), but preferably, it is represented by the following formula: wherein R 3 ' and R 4 ' each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; nb represents 1 to 8; and when nb is two or more, each Rs' and R 4 ' may be the same or different.
  • the alkyl group represented by R s ' and R 4 ' may be straight or branched, and may include, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and a tert-butyl group.
  • R 1 in the formula (BAR-A) there may be mentioned a group having the same meaning as which is described as the preferred group of the above Rbi.
  • Rb 1 preferred examples as Rb 1 are shown. -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -,
  • bleaching accelerator group represented by -S-Rbi-Rb 2 particularly preferred are -S-CH 2 CH 2 COOH, -S-CH 2 CH 2 CH 2 COOH,
  • R 7 and Rs each represent an alkyl group, a cycloalkyl group, an aryl group, a hetero ring or a halogen atom
  • the alkyl group, the cycloalkyl group, the aryl group and the hetero ring described above may be bonded through an oxygen atom, a nitrogen atom or a sulfur atom.
  • the alkyl group, the cycloalkyl group, the aryl group and the hetero ring described above may be bonded through the following bonding groups.
  • these groups may be bonded through each group of acylamino, carbamoyl, sulfonamide, sulfamoyl, sulfamoylcarbonyl,carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone and sulfonyloxy.
  • the alkyl group, the cycloalkyl group, the aryl group and the hetero ring described above may include those having substituent groups described below.
  • substituent groups there may be mentioned, for example, a halogen atom, each group of nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamide, hetero ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imide and acyl.
  • R 7 and R s may be the same or different.
  • R 7 and R 8 have the same meanings as R 7 and R 8 in the formulae (II) and (III), respectively.
  • R 7 and R 8 have the same meanings as R 7 and R 8 in the formulae (II) and (III), respectively.
  • R s represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group or a heterocyclic group
  • Z represents a group of non-metallic atoms necessary for forming 5- to 7-membered carbon rings (e.g.
  • R s and X have the same meanings as R 9 and X in the formula (XI), respectively; and R 11 represents an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylamino group, a dialkylamino group or an anilino group.
  • R 12 and R 13 may be the same or different, and each represent an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, an ammonium group or where A represents a group of non-metallic atoms necessary for forming 5- to 7-membered hetero rings (e.g. phthalimide, triazole and tetrathiazole) with a nitrogen atom.
  • R 14 represents, for example, an alkyl group, an aryl group, an anilino group, an alkylamino group or an alkoxy group
  • B represents an oxygen atom, a sulfur atom or a nitrogen atom.
  • the TIME useful for practicing the present invention may include those represented by the following formulae (XV), (XVI) and (XVII), but the present invention is not limited to these.
  • X represents a benzene ring which may have a substituent group or a group of atoms necessary for forming a naphthalene ring
  • Y represents -0-, -S- or and is bonded to a coupling position of the coupler residue represented by Cp in the formulae (BAR-A) and (BAR-B)
  • R 15 , R 16 and R 17 each represent a hydrogen atom, an alkyl group or an aryl group
  • a 5 group is substituted with Y at an ortho-position or a para-position, and bonded to an oxygen atom of a bleaching accelerator group.
  • R 18 represents, for example, a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group and a heterocyclic residue
  • R 19 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, an acid amide group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group and a cyano group; and this timing group is bonded to a coupling position of the coupler residue represented by Cp in the formulae (BAR-A) and (BAR-B) by Y similarly as in the formula (XV), and to an oxygen atom of a bleaching acceralator group by a group.
  • an example of the timing group which releases a bleaching accelerator group by the intermolecular nucleophilic substitution reaction is represented by the formula (XVII).
  • Nu is a nucleophilic group having an oxygen, sulfur or nitrogen atom abundant in electrons, and bonded to a coupling position of the coupler residue represented by Cp in formulae (BAR-A) and (BAR-B);
  • E is an electrophilic group having a carbonyl group, a thiocarbonyl group, a phosphinyl group or a thiophosphinyl group insufficient in electrons, and bonded to an oxygen atom of a bleaching accelerator group;
  • X makes a stereographic relationship between Nu and E, and is a bonding group which undergoes the intermolecular nucleophilic substitution reaction accompanied with formation of a 3-membered ring or a 7-membered ring after Nu is released from the coupler residue represented by Cp in the formulae (BAR-A) and (BAR-B
  • timing group may include the following compounds.
  • a silver halide emulsion to be used in the light-sensitive material for negative images there may be preferred a silver halide emulsion containing silver halide grains which are constituted of two or more phases having different silver iodide contents, and have said average silver iodide content higher than the silver iodide content of a peripheral phase thereof.
  • the state that the average silver iodide content of the grains is higher than the silver iodide content of the peripheral phase of the grains can be measured according to the following method.
  • the silver halide emulsion is an emulsion containing silver halide grains having an average value of grain size/grain thickness of less than 5
  • an average silver iodide content (Ji) obtained by an X-ray fluorescence analysis and a silver iodide content of a grain surface (J 2 ) obtained by an X-ray excited photoelectron spectroscopy are compared, the relationship of J,>J 2 is satisfied.
  • the grain size herein mentioned is a diameter of a circumscribed circle of a plane which has a maximum projected area of the grain.
  • an emulsion Prior to a measurement by the X-ray excited photoelectron spectroscopy, an emulsion is pretreated in the following manner. First, a pronase solution is added to the emulsion, and stirred at 40 ° C for 1 hour to effect gelatin degradation. Subsequently, after centrifugation was carried out to precipitate emulsion grains, a supernatant was removed, and then an aqueous pronase solution was added to effect gelatin degradation again under the above conditions. This sample was subjected again to centrifugation, a supernatant was removed, and then distilled water was added to redisperse the emulsion grains in distilled water, followed by centrifugation and removal of a supernatant. After this washing operation was repeated three times, the emulsion grains were redispersed in ethanol. The solution obtained was coated thinly on a silicone wafer applied with mirror polishing to give a sample for measurement.
  • ESCA/SAM Model 560 (trade name) manufactured by PHI Co. is used as a device, and the measurement is conducted under the conditions of X-rays for excitation of Mg-K ⁇ rays, an X-ray source voltage of 15 KV, an X-ray source current of 40 mA and a pass energy of 50 eV.
  • a composition ratio is calculated by using integral intensities of the respective peaks according to the relative sensitivity coefficient method.
  • a grain size distribution is preferably monodispersed.
  • the monodispersed silver halide emulsion refers to an emulsion in which a weight of silver halide included within the range of ⁇ 20 % of its grain size with an average grain size r as a center is 60 % or more, preferably 70 % or more, more preferably 80 % or more of a total weight of silver halide grains.
  • the average grain size r is defined as a grain size ri when the product of ni which is frequency of grains having a grain size of ri and ri 3 (ni x ri 3 ) becomes maximum (effective number of 3 digits, a number of a minimum digit is rounded).
  • the grain size mentioned here is its diameter, and when the silver halide grain has a shape other than sphere, it is a diameter obtained by converting its projected area to a circle area having the same area.
  • the grain size can be obtained by, for example, photographing said grains magnified at a magnification of 10,000 to 50,000 with an electron microscope, and by measuring a diameter or a projected area of the grains on the print (there should be randomly 1,000 or more grains to be measured on the print).
  • the highly monodispersed emulsion particularly preferred in the present invention is an emulsion having a distribution width of 20 % or less, preferably 15 % or less defined by the following formula:
  • the average grain size and the standard deviation of the grains are determined from ri defined above.
  • the silver halide emulsion is a tabular silver halide emulsion having an average value of grain size/grain thickness of 5 or more
  • an average silver iodide content (J) obtained by the above X-ray fluorescence analysis and an average measured value of a silver iodide content measured on silver halide crystals which are apart by 80 % or more from a central portion relative to a grain size direction of the silver halide grains (J 3 ) according to an X-ray microanalysis are compared, the relationship of J,>J 3 is satisfied.
  • the X-ray microanalysis is explained.
  • a grid for observation with a electron microscope in which an energy dispersion type X-ray analysis device is provided, silver halide grains are dispersed, and a magnification is set by cooling with liquid nitrogen so that there is one grain within a CRT field, and intensities of IL ⁇ rays and AgLa rays for a predetermined time are integrated.
  • intensities of IL ⁇ rays and AgLa rays for a predetermined time are integrated.
  • the average value of grain size/grain thickness is preferably 6 or more and 100 or less, particularly preferably 7 or more and 50 or less.
  • the silver iodide content of the grain surface measured according to the X-ray excited photoelectron spectroscopy is preferably 6 to 0 mole %, more preferably 5 to 0 mole %, particularly preferably 4 to 0.01 mole %.
  • the average measured value of a silver iodide content measured on silver halide crystals which are apart by 80 % or more from a central portion relative to a grain size direction of the silver halide grains (J 3 ) according to the X-ray microanalysis is preferably 6 to 0 mole %, more preferably 5 to 0 mole %, particularly preferably 4 to 0.01 mole %.
  • the average thickness of the tabular silver halide grains is preferably 0.5 to 0.01 ⁇ m, particularly preferably 0.3 to 0.05 ⁇ m.
  • the average grain size of the silver halide grains contained in the tabular silver halide emulsion is preferably 0.5 to 30 ⁇ m, more preferably 1.0 to 20 ⁇ m.
  • the above silver halide emulsion having an average value of grain size/grain thickness of less than 5 is preferably monodispersed, and preferably of a core/shell type.
  • the above tabular silver halide emulsion having an average value of grain size/grain thickness of 5 or more comprises preferably silver iodide existing locally at a central portion of the grain.
  • the core/shell type silver halide emulsion having an average value of grain size/grain thickness of less than 5 comprises silver halide grains having a grain structure comprising two or more phases having different silver iodide contents, in which a phase with the highest silver iodide content (called “core”) is not the most outer layer (called “shell”).
  • the silver iodide content is preferably 6 to 40 mole %, more preferably 8 to 30 mole %, particularly preferably 10 to 20 mole %.
  • the silver iodide content of the most outer phase is preferably less than 6 mole %, more preferably 0 to 4.0 mole %.
  • the rate of the shell portion in the core/shell type silver halide grains is preferably 10 to 80 %, more preferably 15 to 70 %, particularly preferably 20 to 60 % in volume.
  • the rate of the core portion is preferably 10 to 80 %, more preferably 20 to 50 % in volume of the total grains.
  • the difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content may have a sharp borderline or may change continuously without a distinct borderline.
  • silver halide grains having an intermediate phase with an intermediate silver iodide content between the contents of the core portion and the shell portion, between the core and the shell are preferably used.
  • the volume of the intermediate layer is preferably 5 to 60 %, more preferably 20 to 55 % of the total grains.
  • the differences in silver iodide content between the shell and the intermediate layer and between the intermediate layer and the core are preferably 3 mole % or more, respectively, and the difference in silver iodide content between the shell and the core is preferably 6 mole % or more.
  • the core/shell type silver halide emulsion is preferably silver iodobromide, and its average silver iodobromide content is preferably 4 to 20 mole %, more preferably 5 to 15 mole %. Further, silver chloride can be contained within the range which does not impair the effect of the present invention.
  • the core/shell type silver halide emulsion can be prepared according to the known methods disclosed in Japanese Unexamined Patent Publications No. 177535/1984, No. 138538/1985, No. 52238/1984, No. 143331/1985, No. 35726/1985 and No. 258536/1985.
  • a halogen composition of the seed grains there can be used any desired composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide and silver chloride, preferably silver iodobromide or silver bromide having a silver iodide content of 10 mole % or less.
  • the rate of the seed grains in total silver halide is preferably 50 % or less, particularly preferably 10 % or less in volume.
  • the distribution state of silver iodide in the above core/shell type silver halide grains can be detected according to various physical measurement methods. For example, it can be determined according to a luminescence measurement at low temperatures and an X-ray diffractometry as described in Summary of Lectures in Meeting of Japan Photographic Society in 1981.
  • the core/shell type silver halide grains may comprise either normal. crystals which are cubic, tetradecahedral or octahedral or twins, and further it may comprise a mixture of these, but preferably normal crystals.
  • the phase with a high iodine content at the central portion is preferably 80 % or less, particularly 60 % to 10 % of the total volume.
  • the silver iodide content at the central portion is preferably 5 to 40 mole %, particularly preferably 10 to 30 mole %.
  • the phase with a low iodine content with which the phase with a high iodine content at the central portion is surrounded (a peripheral portion) may comprise silver iodobromide preferably having a silver iodide content of 0 to 10 mole %, more preferably 0.1 to 6.0 mole %.
  • the tabular silver halide emulsion comprising silver iodide existing locally at the central portion can be obtained by the known method disclosed in Japanese Unexamined Patent Publication No. 99433/1984.
  • the average silver iodide content of all the silver halide emulsions in the light-sensitive silver halide photographic material for negative images is preferably 0.1 to 15 mole %, more preferably 0.5 to 12 mole %, particularly preferably 1 to 6 mole %.
  • the average grain size of all the silver halide emulsions in the light-sensitive silver halide color photographic material for negative images is 2.0 ⁇ m or less, more preferably 0.1 to 1.0 ⁇ m or less, particularly preferably 0.2 to 0.6 lim.
  • the lower limit of the sum of total dry film thickness of all the hydrophilic colloid layers of the light-sensitive silver halide color photographic material for negative images (hereinafter described as "the film thickness of the emulsion surface") is limited depending on silver halide emulsions, couplers, lubricants and additives contained therein, and the film thickness of the emulsion surface is preferably 5 ⁇ m to 18 ⁇ m, more preferably 10 ⁇ m to 16 ⁇ m.
  • the thickness from the most outer surface of the emulsion surface to the lower end of the emulsion layer which is the nearest to a support is preferably 14 ⁇ m or less, and the thickness to the lower end of the emulsion layer which is different in color sensitivity from said emulsion layer and is the nearest to a support in the second place to said emulsion layer is preferably 10 ⁇ m or less.
  • a method for making a layer of the light-sensitive color material for negative images thinner there may be mentioned a method by reducing a hydrophilic colloid which is a binder. Since a hydrophilic colloid is added for the purposes of maintaining coupler fine oil drops dissolved in silver halide and a high boiling point solvent, preventing increase of fog due to mechanical stress and preventing color contamination caused by diffusion of an oxidized product of a developing agent between layers, it can be reduced to the extent which does not impair these purposes.
  • a method for making a layer thinner there may be mentioned a method by reducing a high boiling point solvent and a method in which an intermediate layer is made thinner by adding a scavenger of an oxidized product of a developing agent to the intermediate layer between layers having different color sensitivities.
  • the total amount of silver halide contained in the light-sensitive silver halide emulsion contained in all the emulsion layers of the light-sensitive silver halide color photographic material for negative images is preferably 6.5 g/m 2 or less, more preferably 2.5 to 6.0 g/m 2 , particularly preferably 3.0 to 5.5 g/m 2 , most preferably 3.5 to 5.0 g /m 2 .
  • the swelled film thickness at the time of development of the totally hydrophilic protective colloid layer provided by coating on a support at an emulsion layer side of the light-sensitive silver halide color photographic material for negative images is preferably 180 % to 350 %, particularly preferably 200 % to 300 % of the dried film thickness.
  • a technique for thus controlling the swelled film thickness is well known in the art, and the thickness can be controlled by selecting, for example, an amount and a kind of a hardener suitably.
  • aldehyde and aziridine type hardeners e.g. those disclosed in PB Report 19,921, U.S. Patents No. 2,950,197, No. 2,964,404, No. 2,983,311 and No. 3,271,175, Japanese Patent Publication No. 40898/1971, and Japanese Unexamined Patent Publication No. 91315/1975
  • isoxazole type hardeners e.g. those disclosed in U.S. Patent No. 331,609
  • epoxy type hardeners e.g. those disclosed in U.S. Patent No. 3,047,394, West German Patent No. 1,085,663, U.K. Patent No. 1,033,518 and Japanese Patent Publication No.
  • vinyl sulfone type hardeners e.g. those disclosed in PB Report 19,920, West German Patents No. 1,100,942, No. 2,337,412, No. 2,545,722, No. 2,635,518, No. 2,742,308 and No. 2,749,260, U.K. Patent No. 1,251,091, Japanese Unexamined Patent Publications No. 150556/1971 and No. 3450/1975, U.S. Patents No. 3,539,644 and No. 3,490,911), acryloyl type hardeners (e.g. those disclosed in Japanese Unexamined Patent Publication No. 154675/1974 and U.S. Patent No.
  • carbodiimide type hardeners e.g. those disclosed in U.S. Patents No. 2,938,892, No. 4,043,818 and No. 4,061,499, Japanese Patent Publication No. 38715/1971 and Japanese Unexamined Patent Publication No. 140154/1974
  • triazine type hardeners e.g. those disclosed in West German Patents No. 2,410,973 and No. 2,553,915, U.S. Patent No. 3,325,287 and Japanese Unexamined Patent Publication No. 12722/1977
  • high molecular type hardeners e.g. those disclosed in U.K. Patent No. 822,061, U.S. Patents No. 3,623,878, No.
  • the swelled film thickness at the time of development is defined as a thickness after dipping for 3 minutes in the following solution maintained at 38 C.
  • the swelled film thickness can be measured according to, for example, a method described in A. Green and G.I.B. Levenson, Journal of Photographic Science, 20, 205 (1972).
  • the swelled film thickness refers to a film thickness measured at 23 ° C and under a controlled humidity of 55 %. Sections of dried samples are enlarged and photographed by a scanning electron microscope, and film thicknesses of the respective layers are measured.
  • the above totally hydrophilic protective colloid layer there may be included in addition to blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers each of which has at least one layer as described above, and further, a protective layer, an antihalation layer, an yellow filter layer and an intermediate layer provided by coating if necessary.
  • the layer structure of the light-sensitive silver halide color photographic material for negative images which can exhibit the effect according to the present invention particularly is a layer structure comprising a colloidal silver antihalation layer, (an intermediate layer), a red-sensitive layer, (an intermediate layer), a green-sensitive layer, (an intermediate layer), a colloidal silver yellow filter layer, a blue-sensitive layer, (an intermediate layer) and a protective layer coated successively in this order from a support, and further a layer structure comprising a colloidal silver antihalation layer, (an intermediate layer), a red-sensitive layer, (an intermediate layer), a green-sensitive layer, (an intermediate layer), a blue-sensitive layer, (an intermediate layer), a red-sensitive layer, (an intermediate layer), a green-sensitive layer, (a colloidal silver yellow filter layer), a blue-sensitive layer, (an intermediate layer) and a protective layer coated successively in this order from a support.
  • the layers in the parentheses may be omitted.
  • the respective layers of the above red-sensitive layer, green-sensitive layer and blue-sensitive layer are preferably divided into high sensitivity layers and low sensitivity layers, respectively.
  • silver halide emulsions may be chemically sensitized by using active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine; selenium sensitizers; reducing sensitizers such as stannous salt, thiourea dioxide and polyamine; noble metal sensitizers such as a gold sensitizer, specifically including potassium aurithiocyanate, potassium chloroaurate and 2-aurothio-3-methylbenzothiazolium chloride, or, for sensitizers of water-soluble groups such as ruthenium, palladium, platinum, rhodium and iridium, specifically including ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladate (some kinds of these act as a sensitizer or a fog restrainer depending on the amount used) singly or in suitable combination (e.g. a combination of a gold sensitizer and a sulfur sensitizer and a combination of a gold sensitizer and
  • the silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and prior to this chemical ripening, during ripening or after ripening, at least one hydroxytetrazaindenes and at least one nitrogen-containing heterocyclic compounds having a mercapto group may be contained in the silver halide emulsion.
  • silver halide may be optically sensitized by adding an appropriate sensitizing dye in an amount of 5 x 10- 8 to 3 x 10- 3 mole per mole of silver halide.
  • an appropriate sensitizing dye in an amount of 5 x 10- 8 to 3 x 10- 3 mole per mole of silver halide.
  • various sensitizing dyes can be used singly or in combination of two or more kinds.
  • the sensitizing dye advantageously used in the present invention there may be mentioned, for example, those mentioned below.
  • sensitizing dye used in the blue-sensitive silver halide emulsion there may be mentioned, for example, those disclosed in West German Patent No. 929,080, U.S. Patents No. 2,231,658, No. 2,493,748, No. 2,503,776, No. 2,519,001, No. 2,912,329, No. 3,656,959, No. 3,672,897, No. 3,694,217, No. 4,025,349 and No. 4,046,572, U.K. Patent No. 1,242,588, and Japanese Patent Publications No. 14030/1969 and No. 24844/1977.
  • sensitizing dye used in the green-sensitive silver halide emulsion there may be typically mentioned, for example, cyanine dyes, merocyanine dyes or composite cyanine dyes disclosed in U.S. Patents No. 1,939,201, No. 2,072,908, No. 2,739,149 and No. 2,945,763 and U.K. Patent No. 505,979.
  • cyanine dyes, merocyanine dyes or composite cyanine dyes disclosed in U.S. Patents No. 2,269,234, No. 2,270,378, No. 2,442,710, No.
  • cyanine dyes, merocyanine dyes or composite cyanine dyes disclosed in U.S. Patents No. 2,213,995, No. 2,493,748 and No. 2,519,001 and West German Patent No. 929,080 can be used advantageously in the green-sensitive silver halide emulsion or the red-sensitive silver halide emulsion.
  • sensitizing dyes may be used singly or in combination of these.
  • an optical sensitization to a desired wavelength region may be effected.
  • spectral sensitization method there may be typically mentioned, for example, methods by using a combination of benzimidazolocarbocyanine with benzoxazolocarbocyanine disclosed in Japanese Patent Publications No. 4936/1968, No. 22884/1968, No. 18433/1970, No. 37443/1972, No. 28293/1973, No. 6209/1974 and No. 12375/1978, and Japanese Unexamined Patent Publications No. 23931/1977, No. 51932/1977, No. 80118/1979, No. 153926/1983, No. 116646/1984 and No. 116647/1984.
  • sensitizing dyes are previously dissolved in a hydrophilic organic solvent, for example, methyl alcohol, ethyl alcohol, acetone, dimethylformamide or fluorinated alcohol disclosed in Japanese Patent Publication No. 40659/1975, and added in the form of a dye solution.
  • a hydrophilic organic solvent for example, methyl alcohol, ethyl alcohol, acetone, dimethylformamide or fluorinated alcohol disclosed in Japanese Patent Publication No. 40659/1975
  • the time of addition may be any desired period such as the time of initiating the chemical ripening of the silver halide emulsion, during the ripening and the time of completion of the ripening, and may be at the step immediately before emulsion coating depending on the case.
  • a dye which is water-soluble or decolored by a color developing solution can be added, and said AI dye may include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.
  • the AI dye which can be used there may be mentioned those disclosed in U.K. Patents No. 584,609 and No. 1,277,429, Japanese Unexamined Patent Publications No. 85130/1973, No. 99620/1974, No. 114420/1974, No.
  • AI dyes are generally used preferably in an amount of 2 x 10- 3 to 5 x 10- 1 mole per mole of silver in the emulsion layer.
  • a compound releasing a development inhibitor in accompaniment with development can be also used in the present invention, and may include, for example, those disclosed in U.S. Patents No. 3,297,445 and No. 3,379,529, West German Patent Application (OLS) No. 2,417,914, and Japanese Unexamined Patent Publications No. 15271/1977, No. 9116/1978, No. 123838/1984 and No. 127038/1984.
  • the DIR compound is a compound which can release a development inhibitor by reaction with an oxidized product of a color developing agent.
  • a representative example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having development inhibition action when eliminated from an active site of the coupler is introduced to an active site of the coupler, and disclosed in, for example, U.K. Patent No. 935,454, U.S. Patents No. 3,227,554, No. 4,095,984 and No. 4,149,886.
  • a coupler mother nucleus forms a dye, and on the other hand, it has property of releasing a development inhibitor.
  • compounds which release a development inhibitor, but not form a dye by coupling reaction with an oxidized product of a color developing agent as disclosed in U.S. Patents No. 3,652,345, No. 3,928,041, No. 3,958,993, No. 3,961,959 and No. 4,052,213, and Japanese Unexamined Patent Publications No. 110529/1978, No. 13333/1979 and No. 161237/1980.
  • timing DIR compound in which a mother nucleus forms a dye or a colorless compound when reacted with an oxidized product of a color developing agent, and on the other hand, a timing group eliminated releases a development inhibitor by the intermolecular nucleophilic substitution reaction or elimination reaction as disclosed in Japanese Unexamined Patent Publications No. 145135/1979, No. 114946/1981 and No. 154234/1982, a so-called timing DIR compound can be also used in the present invention.
  • timing DIR compounds in which the timing group as described above is bonded to a coupler mother nucleus which forms a totally diffusible dye when reacted with an oxidized product of a color developing agent disclosed in Japanese Unexamined Patent Publications No. 160954/1983 and No. 162949/1983 can be also used.
  • the amount of the DIR compound to be contained in the light-sensitive material is preferably in the range of 1 x 10- 4 mole to 10 x 10- 1 mole per mole of silver.
  • the silver halide grains to be used in the case of the light-sensitive color material for positive images have a silver chloride content of 90 mole % or more, a silver bromide content of 10 mole % or less and a silver iodide content of 0.5 mole % or less, and more preferably, the silver halide grains are silver chlorobromide having a silver bromide content of 0.1 to 2 mole %.
  • Said silver halide grains may be used alone or in combination with other silver halide grains having different compositions, and further may be used in combination with silver halide grains having a silver chloride content of 10 mole % or less.
  • the rate of the silver halide grains having a silver chloride content of 90 mole % or more in all the silver halide grains contained in said emulsion layer is 60 % by weight or more, preferably 80 % by weight or more.
  • the above silver halide grains may comprise a uniform composition from an inner portion to an outer portion of the grain, or different compositions between an inner portion and an outer portion of the grain. When compositions are different between an inner portion and an outer portion, the compositions may change continuously or discontinuously.
  • the grain size of the above silver halide grains is not particularly limited, but may be 0.2 to 1.6 w m, more preferably in the range of 0.25 to 1.2 pm in consideration of rapid processing characteristics and other photographic performances such as sensitivity.
  • the above grain size can be measured according to various methods generally used in this technical field.
  • the representative method is described in "Grain Size Analysis Method” (A.S.T.M. Symposium on Light Microscopy, 1955, pp. 94 to 122) by Labland or "Theory of Photographic Process” (written by Meeth and James, 3rd edition, Chapter 2, published by McMillan Co. (1966)).
  • the grain size can be measured by using projected area or an approximate diameter value of the grain.
  • its grain side distribution can be represented fairly precisely as a diameter or projected area.
  • the grain size distribution of the above silver halide grains may be polydispersed or monodispersed.
  • Preferred is a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution of the silver halide grains.
  • the coefficient of variation is a coefficient showing a width of a grain size distribution, and defined by the following formula.
  • ri represents a grain size of each grain
  • ni represents a number of grains.
  • the grain size mentioned here represents its diameter
  • the silver halide grain has a shape other than cube or sphere, it represents a diameter obtained by converting its projected area to a circle area having the same area.
  • the silver halide grains to be used in the above emulsion may be obtained according to any method such as an acidic method, a neutral method and an ammoniacal method. Said grains may be grown at one time or may be grown after seed grains are formed. A method for forming seed grains and a method for growing them may be the same or different.
  • the system for reacting soluble silver salts with soluble halogen salts may be a normal precipitation, a reverse precipitation, a simultaneous precipitation or a mixture thereof, but preferably a simultaneous precipitation.
  • a simultaneous precipitation a pAg controlled double jet method disclosed in Japanese Unexamined Patent Publication No. 48521/1979 can be also used.
  • a silver halide solvent such as thioether may be used.
  • a mercapto group- containing compound, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming the silver halide grains or after completion of forming the grains.
  • the above silver halide grains can have any desired shape.
  • One preferred example is a cube having ⁇ 100 ⁇ phase as a crystalline surface.
  • the silver halide grains according to the present invention may be grains comprising a single shape or a mixture of grains having various shapes.
  • a metal ion such as a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof and an iron salt or a complex salt thereof can be added to be contained internally of the grain and/or on a grain surface.
  • a reducing sensitizing nucleus can be given internally of the grain and/or a grain surface.
  • unnecessary soluble salts may be removed from the emulsion containing the above silver halide grains, or may be contained therein. Said salts can be removed according to a method described in Research Disclosure No. 17643.
  • the above silver halide grains may be a grain of which a latent image is mainly formed on a grain surface or a grain of which a latent image is mainly formed internally of a grain, but preferably a grain of which a latent image is mainly formed on a grain surface.
  • the above emulsion can be chemically sensitized according to a conventional method.
  • the respective silver halide emulsions of the light-sensitive color photographic material for positive images are preferably arranged from a support side in the order of a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler and a red-sensitive silver halide emulsion layer containing a cyan coupler, and in the whole light-sensitive material, it is preferred that a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, a non-light-sensitive intermediate layer containing a UV absorber, a red-sensitive silver halide emulsion layer containing a cyan coupler, a non-light-sensitive layer containing a UV absorber and a protective layer are arranged on a support as essential layers in this order from said support side.
  • UV absorber those represented by the following formula (U) are preferred.
  • R i , R 2 and R 3 each represent a hydrogen atom, a halogen atom, an alkyl gorup, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group and a hydroxyl group.
  • the respective groups represented by R 1 to R 3 include those having a substituent group.
  • a hydrogen atom, an alkyl group, an alkoxy group and an aryl group are preferred, and particularly, a hydrogen atom, an alkyl group and an alkoxy group are preferred.
  • a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group are particularly preferred.
  • At least one of R 1 to R 3 is preferably an alkyl group, and further, at least two of them are preferably alkyl groups. At least one of R 1 to R 3 is preferably a branched alkyl group.
  • the amount to be added of the compound represented by the formula (U) is preferably 0.1 to 300 % by weight, more preferably 1 to 200 % by weight based on a binder in the layer to which said compound is added.
  • various additives for photography can be further contained.
  • an antifoggant for example, an antifoggant, a stabilizer, a UV absorber, a color antistaining agent, a fluorescent brightener, a color image anti-fading agent, an antistatic agent, a hardener, a surfactant, a plasticizer and a lubricant described in Research Disclosure No. 17643.
  • a hydrophilic colloid to be used for preparing the emulsion may include any desired one such as gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose derivatives, starch derivatives and synthetic hydrophilic polymers of homopolymers or copolymers such as polyvinyl alcohol, polyvinylimidazole and polyacrylamide.
  • a baryta paper As a support of the light-sensitive silver halide color photographic material to be used in the present invention, there may be mentioned, for example, a baryta paper, a polyethylene-coated paper, a polypropylene synthetic paper, a transparent support provided with a reflective layer or used in combination with a reflector, for example, a glass plate, polyester films such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film and a polystyrene film, and also other transparent supports used in general.
  • a baryta paper As a baryta paper, a polyethylene-coated paper, a polypropylene synthetic paper, a transparent support provided with a reflective layer or used in combination with a reflector, for example, a glass plate, polyester films such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film and a
  • These supports are selected suitably depending on the use of the light-sensitive material.
  • the amount added in the light-sensitive silver halide photographic material is represented in a number of grams per 1 m 2 unless otherwise indicated, and the amounts of silver halide and colloidal silver are represented by calculating them on silver.
  • Antihalation layer (HC-1)
  • Twelfth layer First protective layer (PRO-1)
  • Second protective layer (PRO-2)
  • a coating aid Su-2 in addition to the compositions as described above, a coating aid Su-2, a dispersing aid Su-3, an antiseptic agent DI-1, a stabilizer Stab-1, and antifoggants AF-1 and AF-2 were added.
  • Monodispersed emulsion in which a small amount of silver iodide is contained in the surface, having an average grain size of 0.45 ⁇ m and an average silver iodide content of 7.5 mole %.
  • Monodispersed emulsion of which the composition is uniform having an average grain size of 0.30 ⁇ m and an average silver iodide content of 2.1 mole %.
  • Monodispersed emulsion in which a small amount of silver iodide is contained in the surface, having an average grain size of 0.81 ⁇ m and an average silver iodide content of 6.1 mole %.
  • Monodispersed emulsion in which a small amount of silver iodide is contained in the surface, having an average grain size of 0.98 ⁇ m and an average silver iodide content of 8.0 mole %.
  • Em-1, Em-3 and Em-4 are silver iodobromide emulsions mainly comprising octahedrons and having a multilayer structure prepared by referring to Japanese Unexamined Patent Publications No. 138538/1985 and No. 245151/1986.
  • Em-1 to Em-4 each had an average value of grain size/grain thickness of 1.0 and had a grain distribution width of 12, 8, 12 and 10 %, respectively.
  • the samples thus prepared were subjected to wedge exposure by using white lights, and then the following development processings were carried out.
  • the color developing solution used had the following composition.
  • the bleaching solution used had the following composition.
  • Color developing solution shown above 250 ml made up to 1 liter with addition of water, adjusted pH suitably as shown in Table 1 with diethanolamine, aqueous ammonia or glacial acetic acid, and made a rate of an ammonium salt in total cations 5 %.
  • the fixing solution used had the following composition.
  • the stabilizing solution used had the following composition.
  • the bleaching solutions prepared by changing a ferric organic acid complex salt, and an amount and a pH thereof as shown in the following Table 1 were stored at 38 ° C for one week. After development processings were carried out, yellow transmission densities at unexposed portions of the film samples after processing were measured, and at the same time, amounts of residual silver at exposed portions by irradiation were measured according to the X-ray fluorescence method. Further, tar generation was examined by observing external appearances of the bleaching solutions after storage. The above results are shown together in Table 1.
  • EDTA ⁇ Fe means a ferric sodium salt of ethylenediaminetetraacetic acid
  • NTA ⁇ Fe a ferric sodium salt of nitrilotriacetic acid
  • CyDTA ⁇ Fe a ferric sodium salt of 1,2-cyclohexanediaminetetraacetic acid
  • EDTMP ⁇ Fe a ferric sodium salt of ethylenediaminetetramethylene-phosphonic acid
  • NTMP ⁇ Fe a ferric sodium salt of nitrilotrimethylenephosphonic acid
  • (A-1) ⁇ Fe a ferric sodium salt of (A-1).
  • (A-4)- ⁇ Fe, (A-7) ⁇ Fe and (A-9) ⁇ Fe mean ferric sodium salts of (A-4), (A-7) and (A-9), respectively.
  • 0 means no tar generation
  • a slight tar generation and X tar generation apparently recognized, and as a number of X is larger, the extent is larger.
  • the rates of ammonium salt were adjusted by changing rates of an ammonium salt and a sodium salt of ferric complex salts and by adding aqueous ammonia.
  • Example 2 The same light-sensitive silver halide color photographic material used in Example 1 except for changing the silver iodobromide emulsions (Em-1 to 4 and the fine silver iodobromide emulsion) in the third, fourth, sixth, eighth, tenth, eleventh and twelfth layers to silver chlorobromide emulsions shown in the following table were used and processed by using the following processing steps and processing solutions, followed by the same evaluation as in Example 2.
  • the color developing solution used had the following composition.
  • Example 2 The same bleaching solution, fixing solution and stabilizing solution as in Example 1 were used. Consequently, substantially the same effect as in Example 2 could be obtained.
  • Example 2 The light-sensitive silver halide color photographic material used in Example 2 was changed to the following light-sensitive color photographic material, and further, processing steps and processing solutions were changed as shown below.
  • the respective layers having the following constitutions were provided by coating to prepare a multi-layer light-sensitive silver halide color photographic material (1).
  • the coating solutions were prepared as shown below.
  • the second layer to seventh layer coating solutions were prepared in the same manner as in the above first layer coating solution.
  • DOP dioctyl phthalate
  • DNP dinonyl phthalate
  • DIDP diisodecyl phthalate
  • PVP polyvinyl pyrrolidone
  • the pAg was controlled according to a method disclosed in Japanese Unexamined Patent Publication No. 45437/1984, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.
  • the above emulsion EMP-1 was chemically ripened at 50 ° C for 90 minutes to obtain a blue-sensitive silver halide emulsion (EmA).
  • the above emulsion EMP-3 was chemically ripened at 60 °C for 90 minutes to obtain a red-sensitive silver halide emulsion (EmC).
  • Example 2 After the samples obtained were subjected to exposure according to a conventional method, the same evaluation as in Example 2 was made by using the following processing steps and processing solutions.
  • Example 2 Although stain was slightly more liable to be generated as compared with the light-sensitive silver halide color photographic material in Example 1, stain generation could be prevented effectively by lowering the rate of an ammonium salt in total cations as described above.
  • Example 2 The evaluation was made in the same manner as in Example 1 except for changing the color developing agent of the color developing solution in Example 1 to 3-methyl-4-amino-N-ethyl-N( ⁇ -methanesulfonamidoethyl)-aniline sulfate.
  • the bleaching replenishing solution used had the following composition.
  • the fixing solution used had the following composition.
  • the fixing replenishing solution used had the following composition.
  • Example 1 As a stabilizing replenishing solution, the stabilizing solution in Example 1 was used.
  • the processing steps, processing time, processing temperature and replenishing amount of the running processing are as shown below. (the replenishing amount is a value per 1 m 2 of the light-sensitive material.)
  • the running processing was carried out until the amount of the bleaching replenishing solution twice as much as the the bleaching tank volume was replenished.
  • the yellow densities at unexposed portions and amounts of residual silver at maximum density portions after completion of the running processing were measured..
  • Example 6 The same evaluation as in Example 6 was made except for using Experiments No. 4-1, No. 4-5, No. 4-6 and No. 4-10 in Example 6 and changing the replenishing amounts of the bleaching solution as shown in Table 5.
  • Example 4 By using the color paper in Example 4, the same evaluation as in Example 7 was made by using the following processing steps and processing solutions. (Processing steps) the same processing steps used in Example 4 (Color developing tank solution)
  • the replenishing amounts of the respective processing solutions were 60 ml/m 2 of the color developing solution, 30 ml/m 2 of the bleaching solution, 60 ml/m 2 of the fixing solution and 250 ml/m 2 of the stabilizing solution per 1 m 2 of the light-sensitive color material.
  • the same evaluation as in Example 7 was made to obtain substantially the same tendency as in Example 7.
  • Example 6 Experiment was carried out in the same manner as in Example 6 except for providing a nozzle made of vinyl chloride having perforations with a diameter of 5 mm in the bleaching processing tank and the fixing processing tank, spraying the processing solutions on an emulsion surface of the light-sensitive material by means of Iwaki Magnet Pump MD-15 (trade name, manufactured by Iwaki Co.), and further changing crossover time between the color developing tank and the bleaching tank from 8 seconds to 5 seconds. As a result, the yellow density at unexposed portions was further lowered by 0.01 to 0.02, and the amount of residual silver was reduced by half.
  • Iwaki Magnet Pump MD-15 trade name, manufactured by Iwaki Co.
  • magenta couplers shown in Table 7 M-20, M-21, M-31, M-46, M-76, M-78 and M-81 were examined, and substantially the same results as shown in Table 7 were obtained.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19910102316 1990-02-21 1991-02-19 Bleaching solution for light-sensitive silver halide color photographic material and processing method using the same Withdrawn EP0450293A3 (en)

Applications Claiming Priority (2)

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JP41549/90 1990-02-21
JP2041549A JP2873850B2 (ja) 1990-02-21 1990-02-21 ハロゲン化銀カラー写真感光材料の処理方法

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EP0450293A2 true EP0450293A2 (fr) 1991-10-09
EP0450293A3 EP0450293A3 (en) 1993-02-10

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0540990A1 (fr) * 1991-11-06 1993-05-12 Konica Corporation Agent de traitement sous forme de tablette et procédé pour le traitement de matériaux photographiques sensibles à la lumière à l'halogénure d'argent
US5580705A (en) * 1991-12-27 1996-12-03 Konica Corporation Method of bleaching silver halide color photographic light-sensitive materials using particular ferric chelates
EP0501479B1 (fr) * 1991-02-28 1997-10-08 Fuji Photo Film Co., Ltd. Solution de blanchiment et procédé de traitement d'un matériau photographique à l'halogénure d'argent pour la photographie en couleur

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2794509B2 (ja) * 1991-02-28 1998-09-10 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料用の漂白液及びそれを用いた処理方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0270217A2 (fr) * 1986-10-08 1988-06-08 Konica Corporation Solution de blanchiment-fixage ayant un bon rendement de traitement et méthode de traitement d'un matériau sensible à la lumière l'utilisant
EP0329086A2 (fr) * 1988-02-15 1989-08-23 Konica Corporation Procédé de formation d'image pour des matériaux à l'halogénure d'argent sensibles à la lumière
EP0329052A2 (fr) * 1988-02-15 1989-08-23 Konica Corporation Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent
EP0329088A2 (fr) * 1988-02-15 1989-08-23 Konica Corporation Procédé de traitement et solution de blanchiment pour des matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière
EP0329003A2 (fr) * 1988-02-15 1989-08-23 Konica Corporation Procédé de formation d'images photographiques en couleur
EP0334317A2 (fr) * 1988-03-25 1989-09-27 Konica Corporation Composition pour traiter un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
JPH026955A (ja) * 1988-06-24 1990-01-11 Konica Corp ハロゲン化銀カラー写真感光材料用処理液及び処理方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0270217A2 (fr) * 1986-10-08 1988-06-08 Konica Corporation Solution de blanchiment-fixage ayant un bon rendement de traitement et méthode de traitement d'un matériau sensible à la lumière l'utilisant
EP0329086A2 (fr) * 1988-02-15 1989-08-23 Konica Corporation Procédé de formation d'image pour des matériaux à l'halogénure d'argent sensibles à la lumière
EP0329052A2 (fr) * 1988-02-15 1989-08-23 Konica Corporation Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent
EP0329088A2 (fr) * 1988-02-15 1989-08-23 Konica Corporation Procédé de traitement et solution de blanchiment pour des matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière
EP0329003A2 (fr) * 1988-02-15 1989-08-23 Konica Corporation Procédé de formation d'images photographiques en couleur
EP0334317A2 (fr) * 1988-03-25 1989-09-27 Konica Corporation Composition pour traiter un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
JPH026955A (ja) * 1988-06-24 1990-01-11 Konica Corp ハロゲン化銀カラー写真感光材料用処理液及び処理方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0501479B1 (fr) * 1991-02-28 1997-10-08 Fuji Photo Film Co., Ltd. Solution de blanchiment et procédé de traitement d'un matériau photographique à l'halogénure d'argent pour la photographie en couleur
EP0540990A1 (fr) * 1991-11-06 1993-05-12 Konica Corporation Agent de traitement sous forme de tablette et procédé pour le traitement de matériaux photographiques sensibles à la lumière à l'halogénure d'argent
US5366853A (en) * 1991-11-06 1994-11-22 Konica Corporation Tablet-shaped processing agent and method for processing silver halide photographic light sensitive materials
US5580705A (en) * 1991-12-27 1996-12-03 Konica Corporation Method of bleaching silver halide color photographic light-sensitive materials using particular ferric chelates

Also Published As

Publication number Publication date
EP0450293A3 (en) 1993-02-10
JPH03243948A (ja) 1991-10-30
JP2873850B2 (ja) 1999-03-24

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