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EP0243866B1 - Verfahren zur Behandlung eines lichtempfindlichen farbphotographischen Halogenidmaterials - Google Patents

Verfahren zur Behandlung eines lichtempfindlichen farbphotographischen Halogenidmaterials Download PDF

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Publication number
EP0243866B1
EP0243866B1 EP19870105906 EP87105906A EP0243866B1 EP 0243866 B1 EP0243866 B1 EP 0243866B1 EP 19870105906 EP19870105906 EP 19870105906 EP 87105906 A EP87105906 A EP 87105906A EP 0243866 B1 EP0243866 B1 EP 0243866B1
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EP
European Patent Office
Prior art keywords
group
hydrogen atom
silver halide
represent
alkyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP19870105906
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English (en)
French (fr)
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EP0243866A3 (en
EP0243866A2 (de
Inventor
Moeko Hagiwara Nee Higuchi
Shigeharu Koboshi
Satoru Kuse
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Konica Minolta Inc
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Konica Minolta Inc
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Publication date
Priority claimed from JP61093918A external-priority patent/JP2678595B2/ja
Priority claimed from JP9391786A external-priority patent/JPS62250450A/ja
Priority claimed from JP62003452A external-priority patent/JPH07109501B2/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0243866A2 publication Critical patent/EP0243866A2/de
Publication of EP0243866A3 publication Critical patent/EP0243866A3/en
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Publication of EP0243866B1 publication Critical patent/EP0243866B1/de
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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 method for processing a light-sensitive silver halide color photographic material. More particularly, it is concerned with a method for processing a light-sensitive silver halide color photographic material without any impairment of recoloring property even if a replenished amount of a bleaching solution is reduced.
  • Processing of light-sensitive materials comprises basically two steps of color development and desilvering and the desilvering step comprises a bleaching and fixing steps or a bleach-fixing step. Besides these steps, rinse processing, stabilizing processing and so on may be added as additional processing steps.
  • an exposed silver halide is reduced to silver and simultaneously an oxidized aromatic primary amine color developing agent is subjected to reaction with a coupler to form a dye.
  • the halogen ion produced by development of a silver halide is dissolved into a developing solution and accumulated therein.
  • the components such as a retarder and the like contained in a light-sensitive silver halide photographic material is dissolved into a color developing solution and accumulated therein.
  • the silver as produced by development is bleached by an oxidizing agent and then all silver salts are removed from a light-sensitive photographic material as soluble silver salts by a fixing agent.
  • inorganic oxidizing agents such as red prussinate, dichromic acid salts and the like have been widely employed as an oxidizing agent for bleaching of an image silver.
  • red prussinate and dichromic acid salts are relatively superior in a bleaching power of image silver, but tend to be decomposed with light to produce a cyan ion and a hexavalent chromium ion, which may be harmful to human beings and show an unfavourable property for prevention of environmental pollution.
  • the processing solution containing such inorganic oxidizing agents has a disadvantage of being difficult to regenerate and reuse the waste after processing without discarding.
  • the processing solution using the organic acid metal complex has a drawback of a slow bleaching speed (or oxidation speed) of the image silver (metallic silver) formed during developing step due to a slow oxidizing power.
  • an (ethylenediamine-tetraacetato)iron (III) complex which is believed to exert a strong bleaching power of aminopolycarboxylic acid metal complexes, has been partially practised as a bleaching solution or a bleach-fixing bath, but it has a drawback of an insufficient bleaching power and a prolonged bleaching step, in a high sensitive light-sensitive silver halide color photographic material containing as a main component a silver bromide or silver iodobromide emulsion, particularly a color paper for photographing, a negative color film for photographing, a color reversal film for photographing and the like, which contain, as a silver halide, silver iodide with a high silver content.
  • a color developing component in previous bath tends to adhere to the light-sensitive material and thereby being brought in and accumulated in a bleaching bath.
  • any means for maintaining a given concentration range of components in a processing bath in order to avoid deterioration of performance of a bleaching solution owing to change in component concentrations As the said means, one has usually adopted a method for repleneishing a replenishing solution to dilute unnecessary increased components and supplement deficient components. By replenishing the replenishing solution, a large volume of overflow tend to be necessarily produced and discarded; this method would pose a great problem economically or in environmental pollution.
  • replenishing solutions are condensed and supplied in a small volume in order to decrease the overflowed solution, so-called a condensed, low replenishing system, or another method wherein a regenerating agent is added to the overflowed solution for reuse as a replenishing solution.
  • a condensed, low replenishing system is favourable by doing a low replenishing with no regeneration step; an extreme decrease in a replenishing amount of a bleaching solution, however, tends to raise a concentration of color developing components taken into a bleaching solution and to receive the influence by concentration with evaporation more easily, which results in more accumulation of color development components.
  • a concentration of color developing components is increased in a bleaching solution, a ratio of contaminating color developing agents as reducing components, sulfites and the like is increased to inhibit bleaching reaction and, more seriously, a color dye, particularly a cyan dye may be easily converted to the corresponding leuco form, whereby there is given a drawback of being insufficient in coloring or readily producing the so-called poor recoloring.
  • This phenomenon may be seen particularly remarkably in a high sensitive light-sensitive material having a high silver level and silver iodide as a main component.
  • Regeneration step is substantially a system for decreasing a replenished amount, but the above-depicted drawback would be difficult to be seen therein, since aeration can be practised, a substantial aeration is effected owing to a prolonged residual time in a stock tank and others except for bleaching tank and a prolonged contact time with air, and a processing time in the prior bleaching step is as long as 6 minutes or longer.
  • bleaching stain may be produced in a light-sensitive material, when a low replenishing of a bleaching solution is made, owing to increased color developing components accumulated in a bleaching solution as explained hereinabove. It is the actual state that a bleaching stain problem has been more and more actualized, as a photofinishing laboratory with a low processing amount, e.g., recent compact photofinishing laboratory has a poor refreshing rate of a bleaching solution with an increased vaporization volume.
  • Another object of this invention is to provide a method for processing a light-sensitive silver halide color photographic material which shows an excellent silver bleaching efficacy and an improved production of leuco cyan dyes.
  • a still another object of this invention is to provide a method for processing a light-sensitive silver halide color photographic material with an improved generation of bleaching stain even in a condensed, low replenishing process.
  • a further object of this invention is to provide a method for processing a light-sensitive silver halide color photographic material with less complicated procedures and less control of processing solutions.
  • a method for processing a light-sensitive silver halide color photographic material having at least one silver halide emulsion layer which comprises subjecting to image-like exposure and subsequently to processing including at least color development step and bleaching step, wherein a bleaching solution employed in said bleaching step contains at least one organic acid ferric complex; and said bleaching solution contains at least one organic acid and said bleaching solution is replenished, characterized in that a light-sensitive silver halide color photographic material is processed wherein at least one layer of said silver halide emulsion layer contains at least one magenta coupler having the general formula (M): wherein Z represents a non-metal atom group necessary to form a nitrogen-containing heterocyclic ring, said ring optionally having a substituent; X represents a hydrogen atom or a substituent eliminable through a reaction with an oxidized product of a color
  • the bleaching solution in this invention contains at least one of the compounds having the general formulae (I) - (IX) as shown below.
  • Q represents a group of atoms necessary for-the formation of a nitrogen-containing heterocyclic ring (including the ring condensed with an unsaturated 5- to 6-membered ring); and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic ring (including the ring condensed with an unsaturated 5- to 6-membered ring) or an amino group.
  • R 2 and R 3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.
  • the compound represented by the above formula may also include an enol form compound and a salt thereof.
  • R 6 and R 7 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl 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 ; provided that R 6 and R 7 may be combined to form a ring.
  • Y 1 represents N- or CH-;
  • B 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 residual group or and n7 represents an integer of 1 to 6.
  • R 8 and R 9 each represent or ; and R 10 represents an alkyl group or -(CH 2 ) n8 SO 3 ⁇ (provided that l represents 0 when R 10 is -(CH 2 )- n8 SO 3 ⁇ , or 1 when it is an alkyl group).
  • G ⁇ represents an anion; and n8 represent an integer of 1 to 6.
  • Q 1 represents a group of atoms necessary for the formation of a nitrogen-containing heterocyclic ring (including the ring condensed with an unsaturated or saturated 5- to 6-membered ring); and R 11 represents a hydrogen atom, an alkali metal atom, or an alkyl group; provided that Q' have the same meaning as defined for Qi.
  • D 1 , D 2 , D 3 and D 4 each represent a simple bond arm, an alkylene group having 1 to 8 carbon atoms or a vinylene group; and q1, q2, q3 and q4 each represent an integer of 0, 1 or 2.
  • the ring formed together with a sulfur atom may be further condensed with a saturated or unsaturated 5- to 6- membered ring, with the exception of elementary sulfur;
  • 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 , -NHS0 2 R 16 , -OCOR 16 or -S0 2 R 16 ; Y 2 represents or a hydrogen atom; and m9 and n9 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
  • Ar represents a divalent aryl group or a divalent organic group formed by combination of an aryl group with an oxygen atom and/or alkylene group
  • B 2 and B 3 each represent a lower alkylene group
  • R 23 , R 24 , R 25 and R 26 each represent a hydroxyl 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 3 represents a hydrogen atom or an alkyl group
  • R 32 represents a hydrogen atom or a carboxyl group.
  • the compounds represented respectively by General Formulae (I) to (IX) preferably used in this invention are compounds generally used as bleach accelerators, which are hereinafter referred to as the bleach accelerators of this invention.
  • Typical examples of the bleach accelerators of this invention may include, for example, the following, but by no means limited to these.
  • At least one layer of said silver halide color photographic material contain a cyan coupler having the general formula (C).
  • C represents a cyan coupler having the general formula (C).
  • R 2 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • R 24 represents an unsubstituted or substituted aryl group
  • Z represents a hydrogen atom or a group eliminatabile through a coupling reaction with an oxidizing product of a N-hydroxyalkyl substituted-p-phenylenediamine derivative developing agent.
  • magenta coupler of formula (M) has at least one aromatic sulfonyl group represented by the following formula in its molecular structure: wherein R represents an aliphatic group, an aryl group or a heterocyclic group; m represents an integer of 1 or 2, R may be identical or different when m is 2; R 2 represents an aliphatic group, an aryl group, a heterocyclic group or when R 3 and R 4 each represent a hydrogen atom, an aliphatic group or an aryl group.
  • the present inventors have found that the aforesaid object of this invention can be accomplished by keeping a free organic acid concentration in a bleaching solution at a molar percent of not more than 10 mole % to the organic acid ferric complex as a bleaching agent in a light-sensitive material.
  • An amount of the present bleaching solution to be replenished is 30 mî to 300 ml per 1 m 2 of a light-sensitive silver halide color photographic material, more preferably 40 ml to 250 mt, most preferably 50 m to 200 ml.
  • the organic acid or organic acid capable of forming the organic acid ferric complex may be suitably an aminocarboxylic acid compound or an amin acid compound, namely the amino compound having at least 2 or more carboxy groups or the amino compound having at least 2 or more phosphonic acid groups; preferably those compounds having the following general formulae (XII) and (XIII).
  • E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R 83 0R 83 0R 83 - or -R 83 ZR 83 -, Z represents ⁇ N-R 83 -A 6 or ⁇ N-A 6 , R 79 to R 83 individually represent a substituted or unsubstituted alkylene group, A 2 to A 6 individually represent a hydrogen atom, -OH, -COOM or -P0 3 M 2 and M is a hydrogen atom or an alkali metal atom.
  • aminocarboxylic acid compounds and aminophosphonic acid compounds there may be mentioned (XII - 1), (XII - 2), (XII - 5), (XII - 8), (XII - 19), (XIII -1), (XIII - 3) and (XIII - 5).
  • An amount of the aminocarboxylic acid or aminophosphonic acid compounds in this invention to be added may be 10 % or less of a molar concentration of the organic acid ferric complex co-existing in a bleaching solution, preferably 0 to 5 %, more preferably 0 to 2 % for still more effective exertion of the present effects.
  • the ferric complex of organic acid according to this invention may be employed as a free acid (a hydroacid), an alkali metal salt such as sodium salt, potassium salt or lithium salt, an ammonium salt, a water-soluble amine salt such as triethanol amine salt, preferably potassium salt, sodium salt or ammonium salt.
  • the ferric complexes may be employed with at least one sort thereof or in combination with 2 or more thereof.
  • the amount to be used may be optionally selected and should be determined depending upon the silver amount of light-sensitive material to be processed, composition of a silver halide and the like; for instance, one may use not less than 0.01 mole per 1 litre of the solution employed, preferably 0.05 to 0.6 mole. And, it is preferred in a replenishing solution to employ a concentration of the solubility as condensed as possible for condensed, low replenishment.
  • Q represents a group of atoms necessary for the formation of a nitrogen-containing heterocyclic ring (including the ring condensed with an unsaturated 5- to 6-membered ring); and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic ring (including the ring condensed with an unsaturated 5- to 6-membered ring) or an amino group.
  • R 2 and R 3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.
  • the compound represented by the above formula may also include an enol form compound and a salt thereof.
  • R 6 and R 7 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl 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 ; provided that R 6 and R 7 may be combined 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 residual group or and n7 represents an integer of 1 to 6.
  • R 8 and R 9 each represent or ; and R 10 represents an alkyl group or -(CH 2 ) n8 SO 3 ⁇ (provided that l represents 0 when R 10 is -(CH 2 )- n8 SO 3 ⁇ , or 1 when it is an alkyl group).
  • G ⁇ represents an anion; and n8 represent an integer of 1 to 6.
  • Q 1 represents a group of atoms necessary for the formation of a nitrogen-containing heterocyclic ring (including the ring condensed with an unsaturated or saturated 5- to 6-membered ring); and R 11 represents a hydrogen atom, an alkali metal atom, or an alkyl group; provided that Q' have the same meaning as defined for Qi.
  • D 1 , D 2 , D 3 and D 4 each represent a simple bond arm, an alkylene group having 1 to 8 carbon atoms or a vinylene group; and q1, q2, q3 and q4 each represent an integer of 0, 1 or 2.
  • the ring formed together with a sulfur atom may be further condensed with a saturated or unsaturated 5- to 6- membered ring, with the exception of elementary sulfur;
  • 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 , -NHS0 2 R 16 , -OCOR 16 or -S0 2 R 16 ; Y 2 represents or a hydrogen atom; and m9 and n9 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
  • Ar represents a divalent aryl group or a divalent organic group formed by combination of an aryl group with an oxygen atom and/or alkylene group
  • B 2 and B 3 each represent a lower alkylene group
  • R 23 , R 24 , R 25 and R 26 each represent a hydroxyl 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 3 represents a hydrogen atom or an alkyl group
  • R 32 represents a hydrogen atom or a carboxyl group.
  • the compounds represented respectively by General Formulae (I) to (IX) preferably used in this invention are compounds generally used as bleach accelerators, which are hereinafter referred to as the bleach accelerators of this invention.
  • Typical examples of the bleach accelerators of this invention may include, for example, the following, but by no means limited to these.
  • similarly usable compounds may also include the exemplary compounds disclosed in Japanese Patent Application No. 263568/1985 at page 51 to page 115 of the specification thereof, i.e., Compounds Nos.
  • the compounds having the general formulae (I) to (IX) may be employed alone or in combination with two or more thereof and an amount of the bleaching accelerator to be added to a bleaching solution is usually in the range of 0.01 to 100 g per one litre of the processing solution to give favourable results.
  • an added amount is too small, a bleaching acceleration effect is less, while when an added amount is too large over the required level, precipitates may be formed to stain the light-sensitive silver halide color photographic material to be processed.
  • 0.05 to 50 g per one litre of the processing solution may be preferable, more preferably 0.05 to 15 g per one litre of the processing solution.
  • the present compounds having the above general formulae (I) to (IX) when added to a bleaching solution may be added and dissolved as such, but generally added after previously dissolved in water, an alkali, an organic acid, etc. and, where necessary, they may be added as dissolved in an organic solvent such as methanol, ethanol or acetone to produce no influence upon their bleaching effect and the above-depicted effects.
  • a processing time for bleaching of a light-sensitive silver halide color photographic material with the present bleaching solution is preferably short in order to exert the present effects more effectively.
  • Preferable bleaching time is 6 minutes or shorter, more preferably it is 4 minutes or shorter.
  • the present bleaching solution may be employed at a pH value of 0.2 to 9.5, preferably 2.0 to 8.0, more preferably 4.0 to 7.0.
  • Processing temperature may be 80 ° C or lower, desirably 55 ° C or lower for preventing evaporation and other.
  • the present bleaching solution may contain a halide such as ammonium bromide and the like.
  • the present bleaching solution may contain a pH buffering agent alone or in combination with two or more thereof, said buffering agent comprising various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide and the like.
  • a variety of brightening agents, defoaming agents, surfactants, mildewproofing agents and the like may be incorporated into the bleaching solution.
  • the aromatic primary amine color developing agent which may be preferably employed in the present color developing solution may include various agents widely employed in a variety of color photographic processings. Such developing agents may involve aminophenol- and p-phenylenediamine-type derivatives.
  • These compounds may be generally employed in the form of a salt, e.g., hydrochloride or sulfate rather stable than the free form. They may be usually employed at a concentration of about 0.1 g to about 50 g per one litre of a color developer, more preferably about 1 g to about 1.5 g per one litre of the developer.
  • aminophenol-type developer there may be mentioned, for example, o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-amino-1,4-dimethylbenzene and the like.
  • aromatic primary amine color developing agents in view of the intended objects of this invention are the aromatic primary amine color developing agent containing an amino group having at least one water-soluble group, and the compounds having the following general formula [X] are especially preferred.
  • R represents a hydrogen atom, a halogen atom, or an alkyl group, said alkyl group having a straight or branched chain of 1 to 5 carbon atoms and optionally a substituent.
  • R 14 and R 15 individually represent a hydrogen atom, an alkyl group or an aryl group, said alkyl or aryl group being optionally substituted.
  • alkyl groups there is mentioned preferably an alkyl group substituted with an aryl group.
  • At least one of R 14 and R 15 is an alkyl group substituted with a water-soluble group such as a hydroxy group, a carboxy group, a sulfonic acid group, an amino group, a sulfonamido group and the like or said alkyl group being optionally further substituted.
  • R 16 represents a hydrogen atom or an alkyl group having a straight or branched chain of 1 to 5 carbon atoms and p and q each is an integer of 1 to 5.
  • the p-phenylenediamine derivatives having the above general formula (X) may be employed as salts with an organic or inorganic acid and, for example, one may employ hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, oxalate, benzenedisulfonate and the like.
  • the color developing solution which may be employed in this invention may optionally further contain various components commonly applied, for example, an alkali agent such as sodium hydroxide, sodium carbonate and the like; an alkali metal sulfite; an alkali metal hydrosulfite; an alkali metal thiocyanate, an alkali metal halide; benzyl alcohol; a softening agent; a thickner; a developing accelerator; and the like.
  • an alkali agent such as sodium hydroxide, sodium carbonate and the like
  • an alkali metal sulfite an alkali metal hydrosulfite
  • an alkali metal thiocyanate an alkali metal halide
  • benzyl alcohol benzyl alcohol
  • a softening agent a thickner
  • a developing accelerator and the like.
  • the cyan coupler of this invention can be represented by Formula (C) shown below. wherein R 2 , represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
  • R 2 represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group of methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (such as an allyl group and a heptadecenyl group), a cycloalkyl group, preferably 5- to 7-membered one (for example, cyclohexyl, etc.), an aryl group (for example, a phenyl group, a tolyl group, a naphthyl group, etc.), a heterocyclic group, preferably a group of 5- or 6-membered ring containing 1 to 4 nitrogen atom(s), oxygen atom(s) or sulfur atom(s) (for example, a furyl group, a thienyl group, a benzothiazolyl group, etc.).
  • a desirable substituent may be introduced, for example, an alkyl group having 1 to 10 carbon atoms (for example, methyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.), an aryl group (for example, phenyl, naphthyl, etc.), a halogen atom (such as fluorine, chlorine and bromine), cyano, nitro, a sulfonamide group (for example, methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.), a sulfamoyl group (such as methylsulfamoyl and phenylsulfamoyl) a sulfonyl group (for example, methanesulfonyl, p-toluenesulfonyl, etc.), a fluorosulfonyl
  • R 2 represents a ballast group necessary for imparting diffusion resistance, to the cyan coupler represented by Formula (C) and a cyan dye to be formed from said cyan coupler.
  • it is an alkyl group having 4 to 30 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group.
  • it may include a straight chain or branched alkyl group (for example, t-butyl, n-octyl, t-octyl, n-dodecyl, etc.), a 5- or 6-membered heterocyclic group, etc.
  • R 24 represents a substituted or unsubstituted aryl group (particularly preferably a phenyl group).
  • the substituent in the case when said aryl group have a substituent may include at least one of substituents selected from S0 2 R 25 , a halogen atom (such as fluorine, chlorine, bromine, etc.), -CF 3 , -N0 2 , -CN, -COR 25 , -COOR 25 , -S0 25 OR 25 , -OR 2 s, -OCOR 25 , and
  • R 25 represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group of methyl, ethyl, t-butyl and dodecyl), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (such as an allyl group and heptadecenyl group), a cycloalkyl group, preferably 5- to 7-membered one (for example, cyclohexyl, etc.) an aryl group (for example, a phenyl group, a tolyl group, a naphtyl group, etc.); and R 26 represents a hydrogen atom or the group represented by R 25 .
  • R 25 represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group of methyl, ethyl, t-butyl and dodecyl), an alkenyl group, preferably an alkenyl
  • a preferable compound of the cyan coupler of this invention is a compound such that R 24 is a substituted or unsubstituted phenyl group, and the substituent for the phenyl group is cyano, nitro, -S0 2 R 27 (R 27 is an alkyl group), a halogen atom or trifluoromethyl.
  • ballast group represented by R 21 include a group represented by Formula (C - 1)) shown below.
  • J represents an oxygen atom or a sulfonyl group
  • K represents an integer of 0 to 4
  • R represents 0 or 1
  • R 29 which is present in two or more numbers when K comprises two or more, may be the same or different
  • R 28 represents a straight or branched alkylene group having 1 to 20 carbon atoms and substituted with an aryl group, etc.
  • R 29 represents a monovalent group, preferably, a hydrogen atom, a halogen atom (for example, chlorine, bromine, etc.), an alkyl group, preferably a straight or branched alkyl group having 1 to 20 carbon atoms (for example, each group of methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenetyl, etc.), an aryl group (for example, a phenyl group), a heterocyclic group (for example,
  • Formula (C) Z represents a hydrogen atom or a group eliminatable through a coupling reaction with an oxidized product of the N-hydroxyalkyl substituted-p-phenylenediamine derivative color developing agent.
  • it may include a halogen atom (for example, chlorine, bromine, fluorine, etc.), a substituted or unsubstituted alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxyl group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonamide group, etc., and more specific examples may include those described in U.S.
  • cyan couplers of this invention can be synthesized by known methods, for example, synthesis methods as described in U.S. Patents No. 3,222,176, No. 3,446,622 and No. 3,996,253; British Patent No. 1,011,940; Japanese Unexamined Patent Publications No. 21139/1972, No. 65134/1981, No. 204543/1982 and No. 204544/1982; Japanese Unexamined Patent Publications No. 33250/1983, No. 33248/1983, No. 33249/1983, No. 33251/1983, No. 33252/1983 and No. 31334/1983; Japanese Unexamined Patent Publications No. 24547/1985, No. 35731/1985 and No. 37557/1985; etc.
  • the cyan couplers represented by Formula (C) of this invention may be used alone or in combination of two or more kinds.
  • an amount thereof is usually about 0.005 2 mole, preferably 0.01 to 1 mole per 1 mole of silver halide contained in the silver halide emulsion layer.
  • the photographic material in carrying out the method of the present invention is one which contains, in at least one layer of the silver halide emulsion layer thereof, a magenta coupler represented by the formula (M).
  • the compounds represented by the formula (M) can be also represented specifically by the following formulae (M - I) through (M - VI).
  • R 1 to R 8 and X have the same meanings as the above R and X.
  • magenta couplers represented by the formulae (M - I) to (M - VI) are particularly preferred.
  • R in the formula (M) and R 1 in the formulae (M - I) to (M - VII) should preferably satisfy the following condition 1, more preferably satisfy the following conditions 1 and 2, and particularly preferably satisfy the following conditions 1, 2 and 3:
  • each of R 9 , R 10 and R 11 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, a spiro compound residual group, a bridged hydrocarbon compound residual group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, a sulfonamide group, an imide group, an ureido group, a s
  • R 9 , R 10 and R 11 may be bonded together to form a saturated or unsaturated ring (e.g. cycloalkane ring, cycloalkene ring or heterocyclic ring), and further to form a bridged hydrocarbon compound residual group by bonding R 11 to said ring.
  • a saturated or unsaturated ring e.g. cycloalkane ring, cycloalkene ring or heterocyclic ring
  • the groups represented by R 9 to R 11 may have substituents, and examples of the groups represented by R 9 to R 11 and the substituents which may be possessed by said groups may include examples of the substituents which may be possessed by the R in the above formula (M), and substituents which may be possessed by said substituents.
  • examples of the ring formed by bonding between R 9 and Rio, the bridged hydrocarbon compound residual group formed by R 9 to R 11 and the substituents which may be possesed thereby may include examples of cycloalkyl, cycloalkenyl and heterocyclic groups as mentioned for substituents on the R in the aforesaid formula (M) and substituents thereof.
  • R 9 to R 11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.
  • said alkyl and said cycloalkyl may further have substituents, and examples of said alkyl, said cycloalkyl and subsituents thereof may include those of alkyl, cycloalkyl and substituents thereof as mentioned for the substituents on the R in the formula (M) and the substituents thereof.
  • the magenta coupler represented by formula (M) may include the specific compound enumerated below.
  • Magenta couplers for photography which may be combined with the magenta coupler of this invention may include compounds of pyrazolone type, pyrazolinobenzimidazole type, and indazolone type, etc.
  • the pyrazolone type magenta couplers may include the compounds disclosed in U.S Patents No. 2,600,788, No. 3,062,653, No. 3,127,269, No. 3,311,476, No. 3,419,391, No. 3,519,429, No. 3,558,318, No. 3,684,514 and No. 3,888,680, Japanese Unexamined Patent Publications No. 29639/1974, No. 111631/1974, No. 129538/1974 and No. 13041/1975, Japanese Patent Publications No.
  • nondiffusion colored magenta couplers there may be generally used the compounds arylazo-substituted at the coupling position of a colorless magenta coupler, which may include, for example, the compounds disclosed in U.S. Patents No. 2,801,171, No. 2,983,608, No. 3,005,712 and No. 3,684,514, British Patent No. 937,621, Japanese Unexamined Patent Publications No. 123625/1974 and No. 31448/1974.
  • the colored magenta couplers of the type such that a dye may flow out into a processing solution by the reaction with an oxidized product of a developing agent can be also used.
  • a pyrazoloasol type magenta coupler having at least one aromatic sulfonyl group represented by Formula (A) in the molecular structure.
  • the pyrazoloasol type magenta coupler having at least one aromatic sulfonyl group represented by Formula (A) in the molecular structure employed for this invention may preferably be a magenta coupler represented by the following formula (M).
  • M magenta coupler represented by the following formula (M).
  • Z represents non-metal atoms necessary for formation of a nitrogen-containing heterocyclic ring, the ring formed by said Z may have a substituent
  • X represents a hydrogen atom or a group eliminatable through the reaction with an oxidzed product of a color developing agent
  • R represents a hydrogen atom or a substituent, provided that R is a substituent and/or the ring formed by Z has a substituent, and at least one of said substituent has the group represented by Formula (A).
  • R represents an aliphatic group, an aryl group or a heterocyclic group
  • m represents an integer of 1 or 2
  • R may be the same or different when m is 2.
  • R 2 represents an aliphatic group, an aryl group, a heterocyclic group or (wherein R3 and R4 each represent a hydrogen atom, aliphatic group or an aryl group).
  • the aliphatic group is preferably an aliphatic group having 1 to 36 carbon atoms, including a straight chain or branched alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an alkynyl group and a cycloalkenyl group, and these aliphatic groups may include those having a substituent, which substituent may include the groups other than hydrogen mentioned for the above R.
  • the aryl group may include, for example, a phenyl group, a naphthalene group, etc., and may include those having a substituent, which substituent may include the groups other than hydrogen mentioned for the above R.
  • the heterocyclic group may preferably include a 5- to 7-membered ring containing at least one selected from 1 to 4 nitrogen atom(s), oxygen atom(s) and sulfur atom(s) (for example, a furyl group, a thienyl group, a pyrimidinyl group, an imidazolyl group, a pyrazolyl group, a benzothiazolyl group, a piperidino group, a morpholino group, a benzimidazolyl group, triazolyl group, a triazine group, etc.).
  • These may include those having a substituent, which substituent may include the groups other than hydrogen mentioned for the above R.
  • the group of may preferably include a di-substituted amino group substituted with an aliphatic group or aryl group.
  • R 12 and R 13 each represent a group having the same meaning as defined for R and R 2 in Formula (A).
  • R 12 is an alkyl group.
  • R 13 is an aryl group substituted with an alkoxy group.
  • magenta coupler used in this invention are shown below, but by no means limited to these.
  • the pyrazoloazole type magenta coupler having at least one aromatic sulfonyl group represented by Formula (A) in the molecular structure of this invention can be synthesized by making reference to Journal of the Chemical Society, Perkin I (1977), 2047-2052, U.S. Patent No. 3,725,067, Japanese Unexamined Patent Publications No. 99437/1984, No. 42045/1983, No. 162548/1984, No. 171956/1984, No. 33552/1985, No. 43659/1985, No. 172982/1985 and No. 190779/1985, etc.
  • the pyrazoloazole type magenta coupler of this invention can be used generally in the range of 1 x 10- 3 mole to 1.5 moles, preferably 1 x 10- 2 mole to 1 mole, per mole of silver halide.
  • the pyrazoloazole type magenta coupler of this invention can be used in combination with other type of magenta couplers.
  • the pyrazoloazole type magenta coupler of this invention may be added to a desired hydrophilic colloid layer after dissolving it in an organic solvent having a high boiling point of about 150°C or more optionally together with a low boiling solvent and/or a water soluble organic solvent and effecting emulsification dispersion of the solution in a hydrophilic binder such as an aqueous gelatin solution with use of a surface active agent. There may be inserted a step of removing the dispersing solution, or at the same time of the dispersion, the low boiling organic solvent.
  • Z 11 and Z 21 individually represent atom groups required for forming a benzene or naphthalene ring condensed to an oxazole ring.
  • R41 and R 42 indivually represent an alkyl group, an alkenyl group, or an aryl group,
  • R 43 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
  • X 1 - represents an anion, and n is 1 or 0.
  • Z 11 and Z 2 each represent a group of atoms necessary for the formation of a benzene ring or naphthalene ring condensed with an oxazole ring.
  • the heterocyclic ring to be formed may be substituted with a substituent of various types, and these substituents may preferably include a halogen atom, an aryl group, an alkenyl group, an alkyl group and an alkoxy group. More preferable substituents are a halogen atom, a phenyl group and a methoxy group, and the most preferable substituent is a phenyl group.
  • Z 11 and Z 2 both represent benzene rings condensed with oxazole rings, respectively, and at least one benzene ring of these benzene rings is substituted with a phenyl group at the 5-position thereof and with a halogen atom at the 5-position of the other benzene ring.
  • R41 and R 42 each represent an alkyl group, an alkenyl group or an aryl group, and preferably represent an alkyl group. More preferably, R 41 and R 42 each represent an alkyl group substituted with a carboxyl group or sulfo group, and most preferably, a sulfoalkyl group having 1 to 4 carbon atoms.
  • R 43 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably represent a hydrogen atom or an ethyl group.
  • X 1 - represents an anion; and n represents 0 or 1.
  • the sensitizing dye represented by General Formula (XI), used in this invention can also be used in combination with other sensitizing dyes as a so-called supersensitizing combination.
  • the respective sensitizing dyes may be dissolved in solvents of the same or different type, and these solutions may be mixed prior to the addition to an emulsion or separately added to the emulsion. When they are separately added, the order and the time interval may be arbitrarily determined depending on the purpose.
  • sensitizing dye represented by General Formula (XI) are shown below, but the sensitizing dyes used in this invention are by no means limited to these compounds.
  • the sensitizing dye having the above general formula (XI) may be added to an emulsion at any point during the preparation of the emulsion and preferably during or after chemical ripening.
  • An amount of the dye to be added may be preferably 2 x 10- 6 mole to 1 x 10- 3 mole per 1 mole of a silver halide, more preferably 5 x 10- 6 mole to 5 x 10- 4 mole per 1 mole of the halide.
  • the silver halide emulsion which may be employed in this invention, there may be any emulsion using any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide or silver chloroiodobromide.
  • the protective colloid for these silver halides one may use natural products such as gelatin and the like or various synthetic products.
  • the silver halide emulsion may also contain conventional photographic additives such as a stabilizer, a sensitizer, a hardening agent, a sensitizing dye, a surfactant and others.
  • the processing method according to this invention may be applicable to light-sensitive silver halide color photographic materials such as a color paper, a negative color film, a positive color film, a color reversal film for slide, a color reversal film for motion picture, a color reversal film for TV or a color reversal paper, .
  • the present method is most suited to processing of a high-sensitive light-sensitive color photographic material containing the silver iodobromide or chloroiodobromide containing 0.1 mole % or more of silver iodide and having a total coated silver amount of not less than 20 mg/dm 2.
  • An antihalation coating layer and a gelatin layer were coated over a triacetate film base and there were then coated thereover, in turn, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, a blue-sensitive silver halide emulsion layer and a protective layer so that a total silver amount may become 60 mg per 100 cm 2.
  • Said emulsion layers contained individually a mole % of silver iodide of about 4.5 % of silver iodobromide, while the following yellow coupler (Y - 1) was applied for the blue-sensitive silver halide emulsion layer, the following magenta coupler (M' - 1) for the green-sensitive silver halide emulsion layer and the following cyan coupler (C' - 1) for the red-sensitive silver halide emulsion layer, respectively.
  • the color developing solution, bleaching solution, fixing solution and stabilizing solution as prescribed below were employed.
  • the bleaching replenisher, fixing replenisher and stabilizing replenisher were used with the same compositions as in the respective tank solutions. Also, concentrations of the ethylenediaminetetraacetic acid as one example of the organic acid involved in the bleaching solution varied as indicated in the following Table 1.
  • the color development replenisher was supplied to the color developing solution at 1.5 R per 1 m 2 of the negative color film and the fixing replenisher to the fixing bath at 1 R per 1 m 2 of the negative color film. Also, the stabilizing replenisher was supplied at 1 R per 1 m 2 of the negative color film and washing water was flown at 15 l per 1 m 2 of the film.
  • the bleaching replenisher was supplied at a replenished volume as indicated in the following Table 1.
  • An antihalation layer and a gelatin layer were coated over a triacetate film base and there were then coated thereover, in turn, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, a blue-sensitive silver halide emulsion layer and a protective layer so that a total silver amount may beocme 72 mg per 100 cm 2.
  • Said emulsion layers contained individually a mole % of silver iodide of about 4.3 % of silver iodobromide, while the yellow coupler (Y - 1) as used in Comparative Example 1 was used for the blue-sensitive silver halide emulsion layer, the said Exemplary magenta coupler (M - 5) for the green-sensitive silver halide emulsion layer and the cyan coupler (C'-1) as used in Comparative Example 1 for the red-sensitive silver halide emulsion layer.
  • Comparative samples were prepared by replacing the magenta coupler (M - 5) employed for the film sample of Example 2 with the comparative magenta coupler (M' - 1) as used in Example 2 and the comparative magenta coupler (M' - 2) as shown below repspectively.
  • the film samples of this invention were similarly prepared by using the Exemplary magenta couplers (M - 18), (M - 44), (M - 59), (M - 7), (M - 22), (M - 104), (M - 127) and (M - 1), respectively.
  • the samples using the present magenta couplers showed in every case less magenta stain by 0.04 to 0.06, as compared with the magenta coupler out of the present invention.
  • Example 2 Following the same procedures as in Example 2, there were prepared film samples, except that the Exemplary Compound (XI - 1) or (X - 4) was applied to the green-sensitive silver halide emulsion layer of the film sample prepared by Example 1, and then the same tests as in Example 2 were effected. As a result, a residual silver amount was reduced by 5 to 10 % when the present bleaching solution was applied.
  • An antihalation coating layer and a gelatin layer were coated over a triacetate film base and there were then coated thereover, in turn, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, a blue-sensitive silver halide emulsion layer and a protective layer so that a total silver amount may become 65 mg per 100 cm 2.
  • Said emulsion layers contained individually a mole % of silver iodide of about 4.2 % of silver iodobromide, while the above-mentioned yellow coupler (Y - 1) was applied for the blue-sensitive silver halide emulsion layer, the above-mentioned Exemplary magenta coupler (M - 203) for the green-sensitive silver halide emulsion layer and the above-mentioned cyan coupler (C' - 1) for the red-sensitive silver halide emulsion layer, respectively.
  • M - 203 magenta coupler
  • C' - 1 red-sensitive silver halide emulsion layer
  • the color developing solution, bleaching solution, fixing solution and stabilizing solution as prescribed below were employed.
  • the bleaching replenisher, fixing replenisher and stabilizing replenisher were used with the same compositions as in the respective tank solutions. Also, concentrations of the ethylenediaminetetraacetic acid as one example of the organic acid involved in the bleaching solution varied as indicated in the following Table 4.
  • the color development replenisher was supplied to the color developing solution at 1.5 R per 1 m 2 of the negative color film and the fixing replenisher to the fixing bath at 1 R per 1 m 2 of the negative color film. Also, the stabilizing replenisher was supplied at 1 R per 1 m 2 of the negative color film and washing water was flown at 15 l per 1 m 2 of the film.
  • the bleaching replenisher was supplied at a replenished volume as indicated in the following Table 4.
  • Comparative samples were prepared by replacing the magenta coupler (M - 203) employed for the film sample of Example 6 with the comparative magenta coupler (M' - 1) as used in Example 1 and the comparative magenta coupler (M' - 2) as used in Example 3. Also, the film samples of this invention were similarly prepared by using the Exemplary magenta couplers (M - 200), (M - 216), (M - 220), (M - 228), (M - 233), (M - 235), (M - 239), (M - 205), (M - 209) and (M - 245) respectively. After storing for 3 days, processing was carried out by using the bleaching solution of Example 6, test No. 69. Cyan dye density and residual silver amount were measured. Also, magenta stain in unexposed portion was measured.
  • the samples using the present magenta couplers showed in every case less magenta stain by 0.04 to 0.06, as compared with the magenta coupler out of the present invention.
  • Example 7 Following the same procedures as in Example 6, there were prepared film samples, except that the Exemplary Compound (XI - 1) (XI - 4), (XI - 6) and (XI - 11) were applied to the green-sensitive silver halide emulsion layer of the film sample prepared by Example 6, and then the same tests as in Example 2 were effected. Results are shown in Table 7.
  • Example 6 The same tests as in Example 6, test Mo. 69 were repeated provided for replacing the color developing agent in the color developing solution used in Example 6, test No. 69 (Examplary No. X-2) with the hydrochlorides (D-1) and (D-2) shown below. Further, similar tests were carried out by replacing the color developing agent (X-2) with a sulfate of (X-1), p-toluenesulfonate of (X-4) and p-toluenesulfonate of (X-11).
  • the bleaching solution was added with the above color developing solution by 35 % based on the total amount of the bleaching soluiton, respectively and the processing was carried out after storing for one week at a room temperature.
  • a residual silver amount and a magenta stain (bleaching stain) of the film samples after the processing were determined and a generation of tar in the bleaching soluiton was observed.
  • the results are shown in Table 8.
  • o no generation of tar
  • A represents a little generation of tar
  • x represents generation of tar to such a degree that a tar adhered to a film.
  • Example 1 was repeated provided for replacing (ethylenediaminetetraacetato) iron (III) complex salt used for the bleaching solution and bleach-fixing solution in Example 1 with iron (III) complex salt of the Examplary compound (XII-4) (1,3-diaminopropanetetraacetate). It was found that a residual silver amount did not genarated at all, 0 mg/100 cm 2 , namely, the property against the residual silver amount was further improved.

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Claims (11)

1. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials mit wenigstens einer Silberhalogenid-Emulsionsschicht, die einer Bild-artigen Belichtung und einer nachfolgenden Behandlung unterzogen wird, die wenigstens eine Farbentwicklungsstufe und eine Bleichstufe einschließt, worin eine in der Bleichstufe verwendete Bleichlösung wenigstens einen Eisen(III)-komplex einer organischen Säure enthält; und wobei die Bleichlösung wenigstens eine organische Säure enthält und die Bleichlösung nachgefüllt wird, dadurch gekennzeichnet, daß ein lichtempfindliches farbfotografisches Silberhalogenidmaterial behandelt wird, worin wenigstens eine Schicht der Silberhalogenid-Emulsionsschicht wenigstens einen Magenta-Kuppler enthält, der die allgemeine Formel (M) hat
Figure imgb0771
worin Z eine Nichtmetall-Atomgruppe ist, die erforderlich ist zur Bildung eines Stickstoff-enthaltenden heterocyclischen Ringes, wobei der Ring gegebenenfalls einen Substituenten hat; X ist ein Wasserstoffatom oder ein durch eine Reaktion mit einem oxidierten Produkt eines Farbentwicklungsmittels eliminierbarer Substituent; und R ist ein Wasserstoffatom oder ein Substituent; daß die organische Säure in einem Bereich von nicht mehr als 10 Mol-% des Gehaltes des Eisen(III)komplexes der organischen Säure enthalten ist, der in der Bleichlösung enthalten ist; und daß die Nachfüllmenge in der Bleichstufe 30 ml bis 300 ml pro 1 m2 des farbfotografischen Silberhalogenidmaterials beträgt.
2. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach Anspruch 1, worin die Bleichlösung wenigstens eine der Verbindungen enthält, die die unten aufgeführten allgemeinen Formeln (I) bis (IX) haben;
Figure imgb0772
worin Q eine Gruppe von Atomen darstellt, die für die Bildung eines stickstoffhaltigen heterocyclischen Ringes (einschließlich des Ringes, der mit einem ungesättigten 5-bis 6-gliedrigen Ring kondensiert ist) erforderlich ist; und R ist ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, eine Cycloalkylgruppe, eine Arylgruppe, ein heterocyclischer Ring (einschließlich des Ringes, der mit einem ungesättigten 5-bis 6-gliedrigen Ring kondensiert ist) oder eine Aminogruppe,
Figure imgb0773
worin R2 und R3 jeweils ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, eine Hydroxygruppe, eine Carboxygruppe, eine Aminogruppe, eine Acylgruppe mit 1 bis 3 Kohlenstoffatomen, eine Arylgruppe oder eine Alkenylgruppe darstellen; A stellt dar
Figure imgb0774
Figure imgb0775
Figure imgb0776
Figure imgb0777
oder eine ni -valente heterocyclische Restgruppe (einschließlich der Gruppe, die mit einem ungesättigten 5-bis 6-gliedrigen Ring kondensiert ist); X stellt dar = S, = 0 oder = NR"; R und R' haben jeweils die gleiche Bedeutung, wie sie für R2 und R3 definiert ist; X' hat die gleiche Bedeutung, wie für X definiert; Z ist ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe, eine Aminogruppe, eine Stickstoff-enthaltende heterocyclische Restgruppe, eine Alkylgruppe oder
Figure imgb0778
M ist ein zweiwertiges Metallatom;
R" ist ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, eine Cycloalkylgruppe, eine Arylgruppe, eine heterocyclische Restgruppe (einschließlich der Gruppe, die mit einem ungesättigten 5-bis 6-gliedrigen Ring kondensiert ist) oder eine Aminogruppe; und n1 bis n6 und m1 bis m5 stellen jeweils eine ganze Zahl von 1 bis 6 dar; B ist eine Alkylengruppe mit 1 bis 6 Kohlenstoffatomen; Y ist -N ( oder -CH ( ; R4 und R5 haben jeweils die gleiche Bedeutung, wie sie für R2 und R3 definiert ist; mit der Maßgabe, daß R4 und R5 jeweils -B-SZ darstellen und daß R2 und R3, R und R' sowie R4 und R5 jeweils zur Bildung eines Ringes kombiniert werden können;
Figure imgb0779
worin R6 und R7 jeweils ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, eine Hydroxygruppe, eine Carboxygruppe, eine Aminogruppe, eine Acylgruppe mit 1 bis 3 Kohlenstoffatomen, eine Arylgruppe, eine Alkenylgruppe oder -B1-S-Z1 repräsentieren; mit der Maßgabe, daß R6 und R7 zur Bildung eines Ringes vereinigt werden können; Y1 stellt N-oder CH- dar; B1 ist eine Alkylengruppe mit 1 bis 6 Kohlenstoffatomen; Z1 ist ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe, eine Aminogruppe, eine Stickstoff-enthaltende heterocyclische Restgruppe oder
Figure imgb0780
und n 7 ist eine ganze Zahl von 1 bis 6;
Figure imgb0781
worin R8 und R9 jeweils darstellen
Figure imgb0782
; und R10 ist eine Alkylgruppe oder -(CH2)n8SO- (vorausgesetzt, daß 1 Null darstellt, wenn R10 die Bedeutung -(CH2)n8SO- hat, oder 1 darstellt, wenn es eine Alkylgruppe ist). G- ist ein Anion; und n8 ist eine ganze Zahl von 1 bis 6;
Figure imgb0783
worin Q1 eine Gruppe von Atomen bedeutet, die für die Bildung eines stickstoffhaltigen heterocyclischen Ringes erforderlich ist (einschließlich des Ringes, der mit einem ungesättigten oder gesättigten 5-bis 6-gliedrigen Ring kondensiert ist); und R11 ist ein Wasserstoffatom, ein Alkalimetallatom,
Figure imgb0784
oder eine Alkylgruppe; mit der Maßgabe, daß Q' die gleiche Bedeutung wie für Q1 definiert hat;
Figure imgb0785
worin Di, D2, D3 und D4 jeweils einen einfachen Bindungsarm, eine Alkylengruppe mit 1 bis 8 Kohlenstoffatom oder eine Vinylengruppe darstellen; und q1, q2, q3 und q4 sind jeweils eine ganze Zahl 0, 1 oder 2, wobei der zusammen mit einem Schwefelatom gebildete Ring weiterhin mit einem gesättigten oder ungesättigten 5-bis 6-gliedrigen Ring kondensiert sein kann, mit Ausnahme von elementarem Schwefel;
Figure imgb0786
Figure imgb0787
worin X2 darstellt -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -C02R16, -SO2R16, -OR16, -NR16R17, -SR16, -SO3R16, -NHCOR16, -NHSO2 R16, -OCOR16 oder -SO2 R16; Y2 bedeutet
Figure imgb0788
oder ein Wasserstoffatom; und m9 und n9 sind jeweils eine ganze Zahl von 1 bis 10; R11, R12, R13, R14, R15, R17 und R18 sind jeweils ein Wasserstoffatom, eine niedere Alkylgruppe, eine Acylgruppe oder
Figure imgb0789
R16 ist eine niedere Alkylgruppe; R19 stellt dar -NR20 R21, -OR22 oder -SR22; R20 und R21 sind jeweils ein Wasserstoffatom oder eine niedere Alkylgruppe; und R22 ist eine Gruppe von Atomen, die für die Bildung eines Ringes in Kombination mit R18 erforderlich ist; R20 oder R11 können mit R18 zur Bildung eines Ringes kombiniert sein; M' ist ein Wasserstoffatom oder ein Kation,
Figure imgb0790
worin Ar eine zweiwertige Arylgruppe oder eine zweiwertige organische Gruppe ist, gebildet durch Kombination einer Arylgruppe mit einem Sauerstoffatom und/oder einer Alkylengruppe; B2 und B3 sind jeweils eine niedere Alkylengruppe; R23, R24, R25 und R26 stellen jeweils eine Hydroxy-substituierte niedere Alkylgruppe dar; und x und y sind jeweils 0 oder 1; G' ist ein Anion; und z ist 0, 1 oder 2,
Figure imgb0791
worin R29 und R30 jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellen; R31 stellt ein Wasserstoffatom oder eine Alkylgruppe dar; R32 stellt ein Wasserstoffatom oder eine Carboxygruppe dar.
3. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach Anspruch 1 oder 2, worin wenigstens eine Schicht des lichtempfindlichen farbfotografischen Silberhalogenidmaterials einen Cyan-Kuppler enthält, der die allgemeine Formel (C) hat:
Figure imgb0792
worin R21 eine Alkylgruppe, eine Alkenylgruppe, eine Cycloalkylgruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellt; R24 ist eine unsubstituierte oder substituierte Arylgruppe; und Z ist ein Wasserstoffatom oder eine Gruppe, die durch eine Kupplungsreaktion mit einem oxidierenden Produkt eines N-Hydroxyalkyl-substituiert-p-phenylendiamin-Derivates als Entwicklungsmittel eliminierbar ist.
4. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach Anspruch 1, 2 oder 3, worin wenigstens einer der Substituenten in der allgemeinen Formel (M) eine aromatische Sulfonylgruppe ist, repräsentiert durch die folgende Formel (A)
Figure imgb0793
worin R eine aliphatische Gruppe, eine Arylgruppe oder eine heterocyclische Gruppe darstellt; m ist eine ganze Zahl 1 oder 2, worin R gleich oder verschieden sein kann, wenn m die Bedeutung 2 hat; R2 ist eine aliphatische Gruppe, eine Arylgruppe eine heterocyclische Gruppe oder
Figure imgb0794
wenn R3 und R4 jeweils ein Wasserstoffatom, eine aliphatische Gruppe oder eine Arylgruppe darstellen.
5. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach einem der Ansprüche 1 bis 4, worin die organische Säure oder die zur Bildung des Eisen(III)komplexes der organischen Säure fähige organische Säure eine Verbindung ist, die durch die folgenden allgemeinen Formeln (XII) oder (XIII) repräsentiert wird:
Figure imgb0795
Figure imgb0796
worin E eine substituierte oder unsubstituierte Alkylengruppe, eine Cycloalkylengruppe, eine Phenylengruppe, -R830R830R83- oder -R83ZR83-, Z ist N-R83-A6 oder N-A6 bedeutet, R79 bis R83 stellen einzeln eine substituierte oder unsubstituierte Alkylengruppe dar, A2 bis A6 stellen einzeln ein Wasserstoffatom, -OH, -COOM oder -P03M2 dar, und M ist ein Wasserstoffatom oder ein Alkalimetallatom.
6. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach Anspruch 5, worin die Verbindung, die durch die Formel (XII) oder (XIII) repräsentiert wird, eine Verbindung ist, die aus der Gruppe ausgewählt ist, bestehend aus:
(XII-1) Ethylendiamintetraessigsäure
(XII-2) Diethylentriaminpentaessigsäure
(XII-4) Propylendiamintetraessigsäure
(XII-5) Triethylentetraminhexaessigsäure
(XII-7) 1,2-Diaminopropantetraessigsäure
(XII-8) 1,3-Diaminopropan-2-ol-tetraessigsäure
(XII-19) Ethylendiamintetraethylenphosphonsäure
(XIII-1) Nitrilotriessigsäure
(XIII-3) Hydroxyethylimino-di-essigsäure
(XIII-5) Nitrilotrimethylenphosphonsäure.
7. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach einem der Ansprüche 1 bis 6, worin die Menge der Bleichlösung, die aufzufüllen ist, 40 ml bis 250 ml pro 1 m2 des lichtempfindlichen farbfotografischen Silberhalogenidmaterials beträgt.
8. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach Anspruch 7, worin die Menge der aufzufüllenden Bleichlösung 50 ml bis 200 ml pro 1 m2 des lichtempfindlichen farbfotografischen Silberhalogenidmaterials beträgt.
9. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach Anspruch 2, worin die Bleichlösung wenigstens eine Verbindung enthält, ausgewählt aus der Gruppe, die aus den durch die Formeln (11), (111), (V) oder (VII) repräsentierten Verbindungen besteht.
10. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach einem der Ansprüche 1 bis 9, worin eine Farbentwicklungslösung, die für die Farbentwicklungsstufe verwendet wird, ein Farbentwicklungsmittel enthält, das durch die folgende Formel (X) repräsentiert wird:
Figure imgb0797
worin R13 ein Wasserstoffatom, ein Halogenatom oder eine Alkylgruppe ist, wobei die Alkylgruppe eine gerade oder verzweigte Kette mit 1 bis 5 Kohlenstoffatomen und gegebenenfalls einem Substituenten hat; R14 und R15 stellen einzeln ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe dar, wobei die Alkyl- oder Arylgruppe gegebenenfalls substituiert sein kann; wenigstens einer der Reste R14 und R15 ist eine Alkylgruppe, die mit einer wasserlöslichen Gruppe substituiert ist, wie einer Hydroxygruppe, einer Carboxygruppe, einer Sulfonsäuregruppe, einer Aminogruppe, einer Sulfonamidogruppe oder mit -[-(CH2)q-O-]p R16 , wobei die Alkylgruppe gegebenenfalls weiterhin substituiert ist; R16 ist ein Wasserstoffatom oder eine Alkylgruppe mit einer geraden oder verzweigten Kette mit 1 bis 5 Kohlenstoffatomen, und p und q sind jeweils eine ganze Zahl von 1 bis 5.
11. Verfahren zur Herstellung eines lichtempfindlichen farbfotografischen Silberhalogenidmaterials nach einem der Ansprüche 1 bis 10, worin das lichtempfindliche fotografische Silberhalogenidmaterial wenigstens eine der Verbindungen enthält, die die allgemeine Formel (XI) haben:
Figure imgb0798
worin Z11 und Z21 jeweils eine Gruppe von Atomen darstellen, die zur Bildung eines Benzenringes oder eines Naphthalenringes, der mit einem Oxazolring kondensiert ist, erforderlich ist; R41 und R42 stellen einzeln eine Alkylgruppe, eine Alkenylgruppe oder eine Arylgruppe dar, R43 ist ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 3 Kohlenstoffatomen, X, - ist ein Anion und n ist 1 oder 0.
EP19870105906 1986-04-23 1987-04-22 Verfahren zur Behandlung eines lichtempfindlichen farbphotographischen Halogenidmaterials Expired - Lifetime EP0243866B1 (de)

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JP93918/86 1986-04-23
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JP61093918A JP2678595B2 (ja) 1986-04-23 1986-04-23 ハロゲン化銀カラー写真感光材料の処理方法
JP9391786A JPS62250450A (ja) 1986-04-23 1986-04-23 ハロゲン化銀カラ−写真感光材料の処理方法
JP62003452A JPH07109501B2 (ja) 1987-01-10 1987-01-10 ハロゲン化銀カラ−写真感光材料の処理方法
JP3452/87 1987-01-10

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US5028517A (en) * 1988-05-23 1991-07-02 Konica Corporation Processing method of silver halide photographic light-sensitive material
DE3939755A1 (de) * 1989-12-01 1991-06-06 Agfa Gevaert Ag Bleichbad
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DE2021518A1 (de) * 1970-05-02 1971-12-02 Agfa Gevaert Ag Photographische Bleich- und Bleichfixierbaeder
GB1473874A (en) * 1974-06-26 1977-05-18 Ciba Geigy Ag Photographic silver halide bleach-fix baths
JPS5814834A (ja) * 1981-07-21 1983-01-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の安定化処理方法
JPS6023857A (ja) * 1983-07-20 1985-02-06 Fuji Photo Film Co Ltd ハロゲン化銀カラ−感光材料の処理方法
AU570081B2 (en) * 1983-11-02 1988-03-03 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
DE3518257A1 (de) * 1984-05-21 1985-11-21 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur verarbeitung eines lichtempfindlichen farbphotographischen materials
US4707434A (en) * 1984-08-20 1987-11-17 Konishiroku Photo Industry Co., Ltd. Color image forming method comprising processing with a bleach-fixing solution
JPS61117541A (ja) * 1984-11-13 1986-06-04 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPH0652407B2 (ja) * 1985-04-21 1994-07-06 コニカ株式会社 ハロゲン化銀カラ−写真感光材料

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