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(11) | EP 0 243 866 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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Method for processing light-sensitive halide color photographic material Verfahren zur Behandlung eines lichtempfindlichen farbphotographischen Halogenidmaterials Méthode de traitement d'un matériau photographique couleur à l'halogénure sensible à la lumière |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
Background of the invention
[0001] 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.
[0002] From FR-A-2 276 613, JP-A-6 117 541, EP-A-0 143 570 and EP-A-0 158 369 photographic processing methods are known which use bleaching solutions comprising an organic ferric complex and an organic acid. From EP-A-0 158 369 it is further known to replenish the bleaching solutions.
[0003] 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.
[0004] In color development, 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. In this course, the halogen ion produced by development of a silver halide is dissolved into a developing solution and accumulated therein. Also, 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. In the desilvering step, 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.
[0005] As a processing solution having a bleaching ability for processing of a light-sensitive silver halide color photographic material, 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.
[0006] With regard to the processing solution having a bleaching ability and containing such inorganic oxidizing agent, there have been indicated several serious drawbacks. For instance, 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. Additionally, the processing solution containing such inorganic oxidizing agents has a disadvantage of being difficult to regenerate and reuse the waste after processing without discarding.
[0007] To the contrary, there has been employed a processing solution containing as an oxidizing agent an organic acid metal complex such as an aminopolycarboxylic acid metal complex and the like for meeting the requirements, e.g., less problem in environmental pollution, rapid processing, simplification and regeneration of waste for reuse. However, 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. For instance, 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.
[0008] Also, by processing the light-sensitive material as above, 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.
[0009] Therefore, in a method for continuously developing a large amount of light-sensitive silver halide photographic materials by means of an automatic developing machine, there is required 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. Accordingly, there have been recently proposed a method wherein such 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.
[0010] With particular respect to a bleaching solution or bath, there has been put to practical use a method wherein the organic acid ferrous complex produced by bleaching a developed silver, e.g., (ethylenediaminetetraacetato)iron (II) complex is oxidized with aeration to (ethylenediaminetetraacetato) iron (III) complex, i.e. the organic acid ferric complex, to which a regenerating agent is then added for supplementing deficient components and the resulting mixture is again used as a replenishing solution.
[0011] However, there has appeared recently the so-called compact photofinishing laboratory (also called "miniphoto-finishing laboratory") for processing in a short time and reducing a cost for collection and delivery, where there is a great need for simplification of processing and also for reduction in the area for installing a developing machine and there is not desired a regeneration step required for complicated working and control and also for a processing space.
[0012] Therefore, 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. Thus, when 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.
[0013] Nevertheless, there has been recently desired a much lower replenishing from demands for lower cost, less environmental pollution and so on. Still further, there has been required even such a service (the so-called 1 Hour Photo) to send back to a user in several hours after received. Under these circumstances, the above-mentioned points have been posing far greater problems.
[0014] Also, another problem is that 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.
[Summary of the invention]
[0015] It is an object of this invention to provide a method for processing a light-sensitive silver halide color photographic material with a rapid bleaching step and a low replenishment.
[0016] 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.
[0017] 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.
[0018] 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.
[0019] The present inventors have made earnest studies to dissolve the aforesaid problems and found that the aforesaid objects of this invention can be accomplished by 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 developing agent; and R represents a hydrogen atom or a substituent; that the organic acid is contained in a range of not more than 10 mole % of the content of said organic acid ferric complex contained in said bleaching solution; and that the replenished amount in said bleaching step is 30 m to 300 m per 1m2 of said silver halide color photographic material.
[0020] As one preferred embodiment of this invention, there is provided the embodiment wherein the bleaching solution in this invention contains at least one of the compounds having the general formulae (I) - (IX) as shown below.
[0021] In the formula, 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.
[0022] In the formula, R2 and R3 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.
A represents;
or an ni -valent heterocyclic residual group (including the group condensed with an
unsaturated 5- to 6- membered ring); X represents = S, = O or = NR". Here, R and R'
each have the same meaning as defined for R2 and R3; X' has the same meaning as defined for X; Z represents a hydrogen atom, an alkali
metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic
residual group, an alkyl group or
M represents a divalent metallic atom; R" represents a hydrogen atom, an alkyl group
having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual
group (including the group condensed with an unsaturated 5- to 6-membered ring) or
an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6. B represents
an alkylene group having 1 to 6 carbon atoms; Y represents -N 〈 or -CH 〈 ; R4 and R5 each have the same meaning as defined for R2 and R3; provided that R4 and R5 each may represent -B-SZ and that R2 and R3, R and R', and R4 and R5 each may be combined to form a ring.
[0023] The compound represented by the above formula may also include an enol form compound and a salt thereof.
[0024] In the formula, R6 and R7 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 -B1-S-Z1; provided that R6 and R7 may be combined to form a ring. Y1 represents N- or CH-; B represents an alkylene group having 1 to 6 carbon atoms; Z1 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.
[0025] In the formula, R8 and R9 each represent
or
; and R10 represents an alkyl group or -(CH2)n8SO3⊖ (provided that ℓ represents 0 when R10 is -(CH2)-n8SO3⊖, or 1 when it is an alkyl group). G⊖ represents an anion; and n8 represent an integer of 1 to 6.
[0026] In the formula, Q1 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 R11 represents a hydrogen atom, an alkali metal atom,
or an alkyl group; provided that Q' have the same meaning as defined for Qi.
[0027] In the formula, D1, D2, D3 and D4 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;
[0028] In the formula, X2 represents -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2R16, -SO2R16, -OR16, -NR16 R17, -SR16, -SO3 R16, -NHCOR16, -NHS02 R16, -OCOR16 or -S02 R16; Y2 represents
or a hydrogen atom; and m9 and n9 each represent an integer of 1 to 10. R11, R12, R13, R14, R15, R17 and R18 each represent a hydrogen atom, a lower alkyl group, an acyl group or
R16 represents a lower alkyl group;
R19 represents -NR20R21, -OR22 or -SR22; R20 and R21 each represent a hydrogen atom or a lower alkyl group; and R22 represents a group of atoms necessary for a ring to be formed by combination with
R18. R20 or R11 may be combined with R18 to form a ring. M' represents a hydrogen atom or a cation.
[0029] In the formula, 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; B2 and B3 each represent a lower alkylene group; R23, R24, R25 and R26 each represent a hydroxyl substituted lower alkyl group; and x and y each represent 0 or 1. G' represents an anion; and z represents 0, 1 or 2.
[0030] In the formula, R29 and R30 each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R3, represents a hydrogen atom or an alkyl group; R32 represents a hydrogen atom or a carboxyl group.
[0031] 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.
[0032] Typical examples of the bleach accelerators of this invention may include, for example, the following, but by no means limited to these.
[0033] As another preferable embodiment of this invention, there is the embodiment wherein at least one layer of said silver halide color photographic material contain a cyan coupler having the general formula (C).
(wherein R2, represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R24 represents an unsubstituted or substituted aryl group; and 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).
[0034] As further preferred embodiment of this invention, there is the embodiment wherein the 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; R2 represents an aliphatic group, an aryl group, a heterocyclic group or
when R3 and R4 each represent a hydrogen atom, an aliphatic group or an aryl group.
[Detailed description of the invention]
[0036] In regeneration of a bleaching solution, a large amount of a free organic acid as a stabilizer has been hithereto incorporated in order to prevent precipitation and decomposition caused by organic acid ferric complex in aeration.
[0037] Now, 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.
[0038] In adopting a condensed, low replenishing method, a contact time with air becomes longer due to a prolonged residual time of a bleaching solution in a stock tank and so on or due to enforced aeration, and it has been found that precipitation or decomposition caused by the organic acid ferric complex can be improved even if a substantial aeration is done. Moreover, it is surprising that there can be also reduced the bleaching stain caused by color developing components accumulated in a bleaching solution, i.e. oxidized products of color developing agents.
[0039] An amount of the present bleaching solution to be replenished is 30 mî to 300 mℓ per 1 m2 of a light-sensitive silver halide color photographic material, more preferably 40 mℓ to 250 mt, most preferably 50 m to 200 mℓ.
[0040] 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).
[0041] In the above formulae, E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R830R830R83- or -R83ZR83-, Z represents N-R83-A6 or N-A6, R79 to R83 individually represent a substituted or unsubstituted alkylene group, A2 to A6 individually represent a hydrogen atom, -OH, -COOM or -P03M2 and M is a hydrogen atom or an alkali metal atom.
[0042] Preferable illustrated compounds having the general formula (XII) and (XIII) are given below.
Illustrated Compound
[0043]
(XII - 1) Ethylenediaminetetraacetic acid
(XII - 2) Diethylenetriaminepentaacetic acid
(XII - 3) Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid
(XII - 4) Propylenediaminetetraacetic acid
(XII - 5) Triethylenetetraminehexaacetic acid
(XII - 6) Cyclohexanediaminetetraacetic acid
(XII - 7) 1,2-Diaminopropanetetraacetic acid
(XII - 8) 1,3-Diaminopropan-2-ol-tetraacetic acid
(XII - 9) Ethyl ether diaminetetraacetic acid
(XII - 10) Glycol ether diaminetetraacetic acid
(XII - 11) Ethylenediaminetetrapropionic acid
(XII - 12) Phenylenediaminetetraacetic acid
(XII - 13) Ethylenediaminetetraacetic acid sodium salt
(XII - 14) Ethylenediaminetetraacetic acid tetra(trimethylammonium)salt
(XII - 15) Ethylenediaminetetraacetic acid tetrasodium salt
(XII - 16) Diethylenetriaminepentaacetic acid pentasodium salt
(XII - 17) Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt
(XII - 18) Propylenediaminetetraacetic acid sodium salt
(XII - 19) Ethylenediaminetetramethylene phosphonic acid
(XII - 20) Cyclohexanediaminetetraacetic acid sodium salt
(XII - 21) Diethylenetriaminepentamethylene phosphonic acid
(XII - 22) Cyclohexanediaminetetramethylene phosphonic acid
(XIII - 1) Nitrilotriacetic acid
(XIII - 2) Iminodiacetic acid
(XIII - 3) Hydroxyethyliminodiacetic acid
(XIII - 4) Nitrilotripropionic acid
(XIII - 5) Nitrilotrimethylene phosphonic acid
(XIII - 6) Iminodimethylene phosphonic acid
(XIII - 7) Hydroxyethyliminodimethylene phosphonic acid
(XIII - 8) Nitrilotriacetic acid trisodium salt
[0044] As particularly preferable compounds for the intended effects of this invention, of these 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).
[0045] 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.
[0046] 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.
[0047] The effect of this invention can be better exhibited and another effect to prevent the precipitation due to the silver in a bleaching solution can be also expected, when the bleaching solution contains at least one of the compounds represented respectively by General Formulae (I) to (IX) shown below, which are therefore preferably used in this invention.
[0048] In the formula, 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.
[0049] In the formula, R2 and R3 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.
A represents;
or an ni -valent heterocyclic residual group (including the group condensed with an
unsaturated 5- to 6- membered ring); X represents = S, = O or = NR". Here, R and R'
each have the same meaning as defined for R2 and R3; X' has the same meaning as defined for X; Z represents a hydrogen atom, an alkali
metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic
residual group, an alkyl group or
M represents a divalent metallic atom; R" represents a hydrogen atom, an alkyl group
having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual
group (including the group condensed with an unsaturated 5- to 6-membered ring) or
an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6. B represents
an alkylene group having 1 to 6 carbon atoms; Y represents -N 〈 or -CH 〈 ; R4 and R5 each have the same meaning as defined for R2 and R3; provided that R4 and R5 each may represent -B-SZ and that R2 and R3, R and R', and R4 and R5 each may be combined to form a ring.
[0050] The compound represented by the above formula may also include an enol form compound and a salt thereof.
[0051] In the formula, R6 and R7 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 -B1-S-Z1; provided that R6 and R7 may be combined to form a ring. Y1 represents N- or CH-; B1 represents an alkylene group having 1 to 6 carbon atoms; Z1 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.
[0052] In the formula, R8 and R9 each represent
or
; and R10 represents an alkyl group or -(CH2)n8SO3⊖ (provided that ℓ represents 0 when R10 is -(CH2)-n8SO3⊖, or 1 when it is an alkyl group). G⊖ represents an anion; and n8 represent an integer of 1 to 6.
[0053] In the formula, Q1 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 R11 represents a hydrogen atom, an alkali metal atom,
or an alkyl group; provided that Q' have the same meaning as defined for Qi.
[0054] In the formula, D1, D2, D3 and D4 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;
[0055] In the formula, X2 represents -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2R16, -SO2R16, -OR16, -NR16 R17, -SR16, -SO3 R16, -NHCOR16, -NHS02 R16, -OCOR16 or -S02 R16; Y2 represents
or a hydrogen atom; and m9 and n9 each represent an integer of 1 to 10. R11, R12, R13, R14, R15, R17 and R18 each represent a hydrogen atom, a lower alkyl group, an acyl group or
R16 represents a lower alkyl group;
R19 represents -NR20R21, -OR22 or -SR22; R20 and R2, each represent a hydrogen atom or a lower alkyl group; and R22 represents a group of atoms necessary for a ring to be formed by combination with
R18. R20 or R11 may be combined with R18 to form a ring. M' represents a hydrogen atom or a cation.
[0056] In the formula, 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; B2 and B3 each represent a lower alkylene group; R23, R24, R25 and R26 each represent a hydroxyl substituted lower alkyl group; and x and y each represent 0 or 1. G' represents an anion; and z represents 0, 1 or 2.
[0057] In the formula, R29 and R30 each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R3, represents a hydrogen atom or an alkyl group; R32 represents a hydrogen atom or a carboxyl group.
[0058] 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.
[0059] Typical examples of the bleach accelerators of this invention may include, for example, the following, but by no means limited to these.
[0060] Besides the bleach accelerators of this invention as exemplified in the above, 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. 1-2, I-4 to -7, I-9 to -13, 1-16 to -21, 1-23, 1-24, 1-26, 1-27, 1-30 to -36, 1-38, II-2 to -5, II-7 to -10, II-12 to -20, II-22 to -25, II-27, II-29 to -33, II-35, II-36, II-38 to -41, II-43, II-45 to -55, II-57 to -60, II-62 to -64, II-67 to -71, II-73 to -79, 11-81 to -84, II-86 to -99, II-101, II-102, 11-104 to -110, II-112 to -119, 11-121 to -124, II-126, II-128 to -144, II-146, II-148 to -155, II-157, III-4, III-6 to -8, III-10, III-11, III-13, III-15 to -18, III-20, III-22, III-23, III-25, III-27, III-29 to -32, III-35, III-36, IV-3, IV-4, V-3 to -6, V-8 to -14, V-16 to -38, V-40 to -42, V-44 to -46, V-48 to -66, V-68 to -70, V-72 to -74, V-76 to -79, V-81, V-82, V-84 to -100, V-102 to -108, V-110, V-112, V-113, V-116 to -119, V-121 to -123, V-125 to -130, V-132 to -144, V-146 to -162, V-164 to -174, V-176 to -184, VI-4, VI-7, VI-10, VI-12, VI-13, VI-16, VI-19, VI-21, VI-22, VI-25, VI-27 to -34, VI-36, VII-3, VII-6, VII-13, VII-19, VII-20, etc.
[0061] 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. In General, however, when 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. Accordingly, 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.
[0062] 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.
[0063] 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.
[0064] 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.
[0065] Generally, the present bleaching solution may contain a halide such as ammonium bromide and the like.
[0066] Also, 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. Further, a variety of brightening agents, defoaming agents, surfactants, mildewproofing agents and the like may be incorporated into the bleaching solution.
[0067] 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.
[0068] 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.
[0069] As the 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.
[0070] Particularly useful 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.
[0071] In this formula, 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. R14 and R15 individually represent a hydrogen atom, an alkyl group or an aryl group, said alkyl or aryl group being optionally substituted. In the case of alkyl groups, there is mentioned preferably an alkyl group substituted with an aryl group. At least one of R14 and R15 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. R16 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.
[0072] Examples of the compounds having the above general formula [X] are given below, but the present compounds are not limited thereto.
[Exemplary Compound]
[0074] 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.
[0075] 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.
[0077] The cyan coupler of this invention can be represented by Formula (C) shown below.
wherein R2, represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
[0078] Herein, R2, 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.).
[0079] Into R2, 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 group, a carbamoyl group (for example, dimethyl carbamoyl group, phenyl carbamoyl group, etc.), an oxycarbonyl group (for example, ethoxycarbonyl, phenoxycarbonyl, etc.), an acyl group (for example, acetyl, benzoyl, etc.) a hetero ring (for example, a pyridyl group, a pyrazolyl, etc.), an alkoxy group, an aryloxy group, an acyloxy group, etc.
[0080] R2, 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. Preferably, it is an alkyl group having 4 to 30 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group. For example, 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.
[0081] In Formula (C), R24 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 S02 R25, a halogen atom (such as fluorine, chlorine, bromine, etc.), -CF3, -N02, -CN, -COR25, -COOR25, -S025 OR25,
-OR2s, -OCOR25,
and
[0082] Herein, R25 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 R26 represents a hydrogen atom or the group represented by R25.
[0083] A preferable compound of the cyan coupler of this invention, represented by Formula (C), is a compound such that R24 is a substituted or unsubstituted phenyl group, and the substituent for the phenyl group is cyano, nitro, -S02 R27 (R27 is an alkyl group), a halogen atom or trifluoromethyl.
[0084] Preferred examples of the ballast group represented by R21 include a group represented by Formula (C - 1)) shown below.
[0085] In the formula, J represents an oxygen atom or a sulfonyl group; K represents an integer of 0 to 4; R represents 0 or 1; and R29 which is present in two or more numbers when K comprises two or more, may be the same or different; R28 represents a straight or branched alkylene group having 1 to 20 carbon atoms and substituted with an aryl group, etc.; and R29 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, a nitrogen-containing heterocyclic group), an alkoxy group, preferably a straight chain or branched alkoxy group having 1 to 20 carbon atoms (for example, each group of methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dedecyloxy group, etc.), an aryloxy group (for example, a phenoxy group), a hydroxyl group, an acyloxy group, preferably an alkylcarbonyloxy group, an arylcarbonyloxy group (for example, an acetoxy group and benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably a straight or branched alkylcarbonyl group having 1 to 20 carbon atoms, more preferably a phenoxycarbonyl group, an alkylthio group, preferably an acyl group having 1 to 20 carbon atoms, more preferably a straight or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably a straight chain or branched alkylcarbamide group having 1 to 20 carbon atoms, a benzenecarbamide group, a sulfonamide group, preferably a straight chain or branched alkylsulfonamide group having 1 to 20 carbon atoms or a benzenesulfonamide group, a carbamoyl group, preferably a straight chain or branched alkylaminocarbonyl group having 1 to 20 carbon atoms or a phenylaminocarbonyl group, sulfamoyl group, preferably a straight chain or branched alkylaminosulfonyl group having 1 to 20 carbon atoms or a phenylaminosulfonyl group, etc.
[0086] In 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. For example, 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. Patent No. 3,741,563, Japanese Unexamined Patent Publication No. 37425/1972, Japanese Patent Publication No. 36894/1973, Japanese Unexamined Patent Publications No. 10135/1975, No. 117422/1975, No. 130441/1975, No. 108841/1976, No. 120343/1975, No. 18315/1977, No. 105226/1978, No. 14736/1979, No. 48237/1979, No. 32071/1980, No. 65957/1980, No. 1938/1981, No. 12643/1981, No. 27147/1981, No. 146050/1984, No. 166956/1984, No. 24547/1985, No. 35731/1985 and No. 37557/1985; etc.
[0087] Specific exemplary compounds for the cyan coupler represented by Formula (C) of this invention are shown below, but by no means limited to these.
[0088] These 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.
[0089] The cyan couplers represented by Formula (C) of this invention may be used alone or in combination of two or more kinds. When the cyan couplers of this invention is contained in a silver halide emulsion layer, 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.
[0090] 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).
[0091] When the substituent (e.g. R, R1 to Rs) on the hetero- cyclic ring in the formula (M) and the formulae (M - I) to (M - VI) as hereinafter described has a moiety of the formula:
(wherein R", X and Z" have the same meanings as R, X and Z in the formula (M)), the so-called bis-form type coupler is formed, which is of course included in the present invention. The ring formed by Z, Z', Z" and Z1 as hereinafter described may also be fused with another ring (e.g. a 5- to 7-membered cycloalkene). For example, R5 and R6 in the formula (M - IV), R7 and R8 in the formula (M - V) may be bonded to each other to form a ring (e.g. a 5- to 7-membered rings).
[0092] The compounds represented by the formula (M) can be also represented specifically by the following formulae (M - I) through (M - VI).
[0093] In the above formulae (M - I) to (M - VI)), R1 to R8 and X have the same meanings as the above R and X.
[0094] Of the compounds represented by the formula (M), those represented by the following formula (M - VII) are preferred.
wherein Ri, X and Z1 have the same meanings as R, X and Z in the formula (M.
[0095] Of the magenta couplers represented by the formulae (M - I) to (M - VI), the magenta coupler represented by the formula (M - I)) is particularly preferred.
[0096] To describe about the substituents on the heterocyclic ring in the formulae (M) and (M - I) to (M - VII), R in the formula (M) and R1 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:
Condition 1: a root atom directly bonded to the heterocyclic ring is a carbon atom,
Condition 2: only one of hydrogen atom is bonded to said carbon atom or no hydrogen atom is bonded to it, and
Condition 3: the bondings between the root atom and adjacent atoms are all single bonds.
[0097] Of the substituents R and R1 on the above heterocyclic ring, most preferred are those represented by the formula (M - VIII) shown below:
[0098] In the above formula, each of R9, R10 and R11 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 sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group or a heterocyclicthio group. At least two of R9, R10 and R11 are not hydrogen atoms at the same time.
[0099] Also, at least two of said R9, R10 and R11, for example, R9 and R10 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 R11 to said ring.
[0100] The groups represented by R9 to R11 may have substituents, and examples of the groups represented by R9 to R11 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.
[0101] Also, examples of the ring formed by bonding between R9 and Rio, the bridged hydrocarbon compound residual group formed by R9 to R11 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.
[0102] Of the groups of the formula (M - VIII), preferred are:
(i) the case where two of R9 to R11 are alkyl groups; and
(ii) the case where one of R9 to R11, for example, R11 is a hydrogen atom and two of the other R9 and R10 are bonded together with the root carbon atom to form a cycloalkyl group.
[0103] Further, preferred in (i) is the case where two of R9 to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.
[0104] Here, 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.
[0105] The magenta coupler represented by formula (M) may include the specific compound enumerated below.
[0106] 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. 47167/1978, No. 10491/1979 and No. 30615/1980. As 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.
[0107] 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, as disclosed in U.S. Patent No. 3,419,391, can be also used.
[0108] In the light-sensitive silver halide photographic material employed for the processing method of this invention, there may preferably be contained a pyrazoloasol type magenta coupler having at least one aromatic sulfonyl group represented by Formula (A) in the molecular structure.
[0109] 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).
wherein 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).
[0110] The aromatic sulfonyl group represented by Formula (A) will be described below in detail Formula (A):
[0111] In the formula, R represents an aliphatic group, an aryl group or a heterocyclic group; m represents an integer of 1 or 2; and R may be the same or different when m is 2. R2 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).
[0112] In Formula (A), to describe R and R2 in further detail, 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.
[0113] Of the aromatic sulfonyl group represented by Formula (A), preferable is the compound represented by the following formula:
[0114] In the formula, R12 and R13 each represent a group having the same meaning as defined for R and R2 in Formula (A).
[0115] More preferable is the compound wherein R12 is an alkyl group. Particularly preferable is the compound wherein R13 is an aryl group substituted with an alkoxy group.
[0116] Typical examples of the magenta coupler used in this invention are shown below, but by no means limited to these.
[0117] 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.
[0118] 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.
[0119] The pyrazoloazole type magenta coupler of this invention can be used in combination with other type of magenta couplers.
[0120] 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.
[0121] As another preferred embodiment of this invention, it has been found out that the object of this invention can be much more effectively accomplished by incorporating into the light-sensitive silver halide photographic material at least one of the compounds having the following general formula (XI).
[0122] In this formula, Z11 and Z21 individually represent atom groups required for forming a benzene or naphthalene ring condensed to an oxazole ring. R41 and R42 indivually represent an alkyl group, an alkenyl group, or an aryl group, R43 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X1- represents an anion, and n is 1 or 0.
[0124] In the formula, Z11 and Z2, 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.
[0125] Preferable embodiment is that Z11 and Z2, 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 R42 each represent an alkyl group, an alkenyl group or an aryl group, and preferably represent an alkyl group. More preferably, R41 and R42 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. Still most preferably, they each are a sulfoethyl group. R43 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably represent a hydrogen atom or an ethyl group. X1 - represents an anion; and n represents 0 or 1.
[0126] 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. In such an occasion, 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.
[0127] Specific examples of the 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.
[0128] 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.
[0129] As 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. As 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.
[0130] 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, . In particular, 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/dm2.
Comparative Example 1
[0131] 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 cm2. 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.
[0132] Further, there may be optionally applied such conventional additives as a high-boiling solvent, a sensitizing dye, a hardening agent, a spreader and the like. The negative color films thus produced were exposed, respectively, according to conventional procedures and then subjected to running processing according to the under-mentioned development processing steps.
[0133] The color developing solution, bleaching solution, fixing solution and stabilizing solution as prescribed below were employed.
[Color developing solution]
[0135] Water was added to make up a 1 litre volume and a pH value was adjusted to 10.06 with potassium hydroxide or 20 % sulfuric acid.
[Bleaching solution and bleaching replenisher]
[0137] Water was added to make up a 1 litre volume and a pH value was adjusted to 6.0 with acetic acid with aqueous ammonia.
[Fixing solution and fixing replenisher]
[0139] Water was added to make up a 1 litre volume and a pH value was adjusted to 7.0 with acetic acid and aqueous ammonia.
[Stabilizing solution and stabilizing replenisher]
[Color development replenisher]
[0143] Water was added to make up a 1 litre volume and a pH value was adjusted to 10.12 with potassium hydroxide or 20 % sulfuric acid.
[0144] 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.
[0145] The color development replenisher was supplied to the color developing solution at 1.5 R per 1 m2 of the negative color film and the fixing replenisher to the fixing bath at 1 R per 1 m2 of the negative color film. Also, the stabilizing replenisher was supplied at 1 R per 1 m2 of the negative color film and washing water was flown at 15 ℓ per 1 m2 of the film. The bleaching replenisher was supplied at a replenished volume as indicated in the following Table 1.
[0146] Continuous running processing was applied to 50 m2 of a negative color film, during which a pH value of the bleaching solution was properly adjusted to pH 6.0. The processed sample after running processing was measured for a density of the cyan dye in the maximum density band by means of "Sakura" photoelectric densitometer PDA-65 (available from Konishiroku Photo Industry Co., Ltd.). Also, recoloring property was determined from a difference in the cyan dye density between the sample and the sample retreated with red prussiate. A residual silver amount in the maximum density band was measured according to a fluorescent X-ray method. The above results are summarized in Table 1.
[0147] As apparent from the results in the above Table 1, recoloring property of cyan dye and desilvering property are greatly deteriorated when a replenished amount of the bleaching solution is reduced to not more than 300 mî per 1 m2 of the negative color film; however, it is shown that the bleaching solution having a concentration of ethylenediaminetetraacetic acid, one example of the organic acids involved in the bleaching solution, within the perview of this invention does show an extremely slight deterioration in both recoloring and desilvering properties, even though a replenished amount of the bleaching solution is greatly lowered.
Example 2
[0148] 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 cm2. 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.
[0149] Further, there may be optionally applied such convenient additives as a high-boiling solvent, a sensitizing dye, a hardening agent, a spreader and the like. The negative color films thus produced were exposed, respectively, according to conventional procedures and then subjected to running processing according to the same development processing steps as in Comparative Example 1 except that a concentration of ethylenediaminetetraacetic acid, one example of the organic acids involved in the bleaching solution, was changed as shown in the following Table 3.
[0150] In the steps, continuous running processing was done for 40 m2 of a negative color film, during which a pH value was properly adjusted to pH 6.0. After completion of the running processing, the processed sample was allowed to stand at 38 ° C for 3 days and then measured for a density of the cyan dye in the maximum density band by means of "Sakura" photoelectric densitometer PDA-65 (available from Konishiroku Photo Industry Co., Ltd.). Recoloring property was also determined from a difference in the cyan dye density between the sample and the sample retreated with a red prussiate solution, while a residual silver amount in the maximum density band was measured. The results are summarized in Table 3.
[0151] As apparent from the results of Table 3, where a replenished amount of the bleaching solution is reduced to not more than 300 ml per 1 m2 of the negative color film, recoloring and desilvering properties of the cyan dye was greatly deteriorated; however, it is seen that both recoloring and desilvering properties can be greatly improved with the bleaching solution wherein a concentration of ethylenediaminetetraacetic acid falls within the range of this invention.
Example 3
[0152] 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. Also, 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. After storing for 3 days, processing was carried out by using the bleaching solution of Example 2, test No. 44. Magenta stain in unexposed portion was measured. As a result, 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 4
[0153] Following the same procedures as in Examples 2, tests were carried out, except that the Exemplary Compounds (II - 28), (II - 144), (III - 34), (III - 2), (III - 38) (V - 71), (V - 75) and (VIII - 1) were applied to the bleaching solutions used in Example 2, test Nos. 41 to 45, respectively, and the bleaching processing time was 2 minutes. As a result, though the bleaching processing time was shortened, a residual silver amount in every case was reduced by about 15 to 20 %.
Example 5
[0154] 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.
Example 6
[0155] 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 cm2. 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. As a supersensitizing agent, the following (Z - 1) was employed.
[0156] Further, there may be optionally applied such conventional additives as a high-boiling solvent, a hardening agent, a spreader and the like. The negative color films thus produced were exposed, respectively, according to conventional procedures and then subjected to running processing according to the under-mentioned development processing steps.
[0157] The color developing solution, bleaching solution, fixing solution and stabilizing solution as prescribed below were employed.
[Color developing solution]
[0159] Water was added to make up a 1 litre volume and a pH value was adjusted to 10.00 with potassium hydroxide or 20 % sulfuric acid.
[Bleaching solution and bleaching replenisher]
[0161] Water was added to make up a 1 litre volume and a pH value was adjusted to 5.9 with acetic acid with aqueous ammonia.
[Fixing solution and fixing replenisher]
[0163] Water was added to make up a 1 litre volume and a pH value was adjusted to 7.0 with acetic acid and aqueous ammonia.
[Stabilizing solution and stabilizing replenisher]
[Color development replenisher]
[0167] Water was added to make up a 1 litre volume and a pH value was adjusted to 10.12 with potassium hydroxide or 20 % sulfuric acid.
[0168] 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.
[0169] The color development replenisher was supplied to the color developing solution at 1.5 R per 1 m2 of the negative color film and the fixing replenisher to the fixing bath at 1 R per 1 m2 of the negative color film. Also, the stabilizing replenisher was supplied at 1 R per 1 m2 of the negative color film and washing water was flown at 15 ℓ per 1 m2 of the film. The bleaching replenisher was supplied at a replenished volume as indicated in the following Table 4.
[0170] Continuous running processing was applied to 40 m2 of a negative color film, during which a pH value of the bleaching solution was properly adjusted to pH 6.0. The processed sample after running processing was measured for a density of the cyan dye in the maximum density band by means of "Sakura" photoelectric densitometer PDA-65 (available from Konishiroku Photo Industry Co., Ltd.). Also, recoloring property was determined from a difference in the cyan dye density between the sample and the sample retreated with red prussiate. A residual silver amount in the maximum density band was measured according to a fluorescent X-ray method. The above results are summarized in Table 4.
[0171] As apparent from the results in the above Table 4, recoloring property of cyan dye and desilvering property are greatly deteriorated when a replenished amount of the bleaching solution is reduced to not more than 300 mî per 1 m2 of the negative color film; however, it is shown that the bleaching solution having a concentration of ethylene-diaminetetraacetic acid, one example of the organic acids involved in the bleaching solution, within the perview of this invention does show an extremely slight deterioration in both recoloring and desilvering properties, even though a replenished amount of the bleaching solution is greatly lowered.
Example 7
[0172] 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.
[0174] As a result, 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.
[0175] There are also found that both the recoloring properties of cyan dye and the residual silver amount were good.
Example 8
[0176] Following the same procedures as in Example 6, tests were carried out, except that the Exemplary Compounds (I - 2), (I - 9), (II - 28), (II - 26), (II - 158) (III - 33), (III - 34), (III - 37), (IV - 1 (V - 71), (V - 185), (V - 186), (VI - 8), (VI - 9), (VII - 3), (VIII - 1), (VIII - 4) and (IX - 1) were applied to the bleaching solutions used in Example 6, test No. 69 in the amount described in Table 6, respectively, and the bleaching processing time was 3 minutes.
[0177] As a result, though the bleaching processing time was shortened, a residual silver amount in every case was reduced.
Example 9
[0178] 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.
[0179] From the result of Table 7, there are found that, in the case where the breaching solution and the sensitizing dye of the present invention were employed in combination, residual silver amount was further reduced by about one third and yellow stain in an unexposed portion.
Example 10
[0180] 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).
[0181] In the above test, 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.
[0182] In Table 8, o represents no generation of tar, A represents a little generation of tar and x represents generation of tar to such a degree that a tar adhered to a film.
[0183] From Table 8, there are found that, by using the color developing agent according to the present invention, desilvering property, bleaching stain and generation of tar are all improved.
Example 11
[0184] 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 cm2, namely, the property against the residual silver amount was further improved.
[0185] Further, the similar experient was carried out by arranging the total added amount in terms of iron salt to 0.37 mole and the mixture ratio of (ethylenediaminetetraacetato) iron (III) complex salt and an iron (III) complex salt of Examplary compound (XII-4) to 1:1 to 2:1. It was also found that a residual silver amount did not genarated at all.
Claims for the following Contracting State(s) : DE
1. 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 developing agent; and R represents a hydrogen atom or a substituent; that the organic acid is contained in a range of not more than 10 mole % of the content of said organic acid ferric complex contained in said bleaching solution; and that the replenished amount in said bleaching step is 30 mî to 300 mî per 1m2 of said silver halide color photographic material.
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 developing agent; and R represents a hydrogen atom or a substituent; that the organic acid is contained in a range of not more than 10 mole % of the content of said organic acid ferric complex contained in said bleaching solution; and that the replenished amount in said bleaching step is 30 mî to 300 mî per 1m2 of said silver halide color photographic material.
2. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 1, wherein said bleaching solution contains at least one of the
compounds having the under-mentioned general formulae (I) to (IX);
wherein 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,
wherein R2 and R3 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; A represents:
or an n -valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6- membered ring); X represents = S, = 0 or = NR"; R and R' each have the same meaning as defined for R2 and R3; X' has the same meaning as defined for X; Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, an alkyl group or
M represents a divalent metallic atom; R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring) or an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6; B represents an alkylene group having 1 to 6 carbon atoms; Y represents -N or -CH 〈 ; R4 and R5 each have the same meaning as defined for R2 and R3; provided that R4 and R5 each may represent -B-SZ and that R2 and R3, R and R', and R4 and R5 each may be combined to form a ring,
wherein R6 and R7 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 -B1-S-Z1; provided that R6 and R7 may be combined to form a ring; Y1 represents N- or CH-; B1 represents an alkylene group having 1 to 6 carbon atoms; Z1 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,
wherein R8 and R9 each represent
; and R10 represents an alkyl group or -(CH2)n8SO3⊖ (provided that ℓ represents 0 when R10 is -(CH2)-n8SO3⊖, or 1 when it is an alkyl group); G⊖ represents an anion; and n8 represents an integer of 1 to 6,
wherein Q1 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 R11 represents a hydrogen atom, an alkali metal atom,
or an alkyl group; provided that Q' have the same meaning as defined for Qi,
wherein Di, D2, D3 and D4 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, said 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;
wherein X2 represents -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2R16, -SO2R16, -OR16, -NR16R17, -SR16, -SO3R16, -NHCOR16, -NHSO2R16, -OCOR16 or -SO2 R16; Y2 represents
or a hydrogen atom; and m9 and n9 each represent an integer of 1 to 10; R11, R12, R13 , R14, R,15, R17 and R18 each represent a hydrogen atom, a lower alkyl group, an acyl group or
wherein 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,
wherein R2 and R3 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; A represents:
or an n -valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6- membered ring); X represents = S, = 0 or = NR"; R and R' each have the same meaning as defined for R2 and R3; X' has the same meaning as defined for X; Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, an alkyl group or
M represents a divalent metallic atom; R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring) or an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6; B represents an alkylene group having 1 to 6 carbon atoms; Y represents -N or -CH 〈 ; R4 and R5 each have the same meaning as defined for R2 and R3; provided that R4 and R5 each may represent -B-SZ and that R2 and R3, R and R', and R4 and R5 each may be combined to form a ring,
wherein R6 and R7 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 -B1-S-Z1; provided that R6 and R7 may be combined to form a ring; Y1 represents N- or CH-; B1 represents an alkylene group having 1 to 6 carbon atoms; Z1 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,
wherein R8 and R9 each represent
; and R10 represents an alkyl group or -(CH2)n8SO3⊖ (provided that ℓ represents 0 when R10 is -(CH2)-n8SO3⊖, or 1 when it is an alkyl group); G⊖ represents an anion; and n8 represents an integer of 1 to 6,
wherein Q1 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 R11 represents a hydrogen atom, an alkali metal atom,
or an alkyl group; provided that Q' have the same meaning as defined for Qi,
wherein Di, D2, D3 and D4 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, said 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;
wherein X2 represents -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2R16, -SO2R16, -OR16, -NR16R17, -SR16, -SO3R16, -NHCOR16, -NHSO2R16, -OCOR16 or -SO2 R16; Y2 represents
or a hydrogen atom; and m9 and n9 each represent an integer of 1 to 10; R11, R12, R13 , R14, R,15, R17 and R18 each represent a hydrogen atom, a lower alkyl group, an acyl group or
R16 represents a lower alkyl group;
R19 represents -NR20R21, -OR22 or -SR22; R20 and R21 each represent a hydrogen atom or a lower alkyl group; and R22 represents a group of atoms necessary for a ring to be formed by combination with
R18; R20 or R11 may be combined with R18 to form a ring; M' represents a hydrogen atom or a cation,
wherein 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; B2 and B3 each represent a lower alkylene group; R23, R24, R25 and R26 each represent a hydroxyl substituted lower alkyl group; and x and y each represent
0 or 1; G' represents an anion; and z represents 0, 1 or 2,
wherein R29 and R30 each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
R3, represents a hydrogen atom or an alkyl group; R32 represents a hydrogen atom or a carboxyl group.
3. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 1 or 2 wherein at least one layer of said light-sensitive silver
halide color photographic material contains a cyan coupler having the general formula
(C):
wherein R2, represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R24 represents an unsubstituted or substituted aryl group; and Z represents a hydrogen atom or a group iliminatable through coupling reaction with an oxidizing product of a N-hydroxyalkyl substituted-p-phenylenediamine derivative developing agent.
wherein R2, represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R24 represents an unsubstituted or substituted aryl group; and Z represents a hydrogen atom or a group iliminatable through coupling reaction with an oxidizing product of a N-hydroxyalkyl substituted-p-phenylenediamine derivative developing agent.
4. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 1, 2 or 3, wherein at least one of the substituents in general
formula (M) represents an aromatic sulfonyl group represented by the following formula
(A)
wherein R represents an aliphatic group, an aryl group or a heterocyclic group; m represents an integer of 1 or 2, R1 may be identical or different when m is 2; R2 represents an aliphatic group, an aryl group, a heterocyclic group or
where R3 and R4 each represent a hydrogen atom, an aliphatic group or an aryl group.
wherein R represents an aliphatic group, an aryl group or a heterocyclic group; m represents an integer of 1 or 2, R1 may be identical or different when m is 2; R2 represents an aliphatic group, an aryl group, a heterocyclic group or
where R3 and R4 each represent a hydrogen atom, an aliphatic group or an aryl group.
5. The method for processing a light-sensitive silver halide color photographic material
as claimed in any of claims 1 to 4, wherein the organic acid or organic acid capable
of forming the organic acid ferric complex is a compound represented by the following
general formulae (XII) or (XIII):
wherein E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R830R830R83- or -R83ZR83-, Z represents N-R83-A6 or N-A6, R79 to R83 individually represent a substituted or unsubstituted alkylene group, A2 to A6 individually represent a hydrogen atom, -OH, -COOM or -P03M2 and M is a hydrogen atom or an alkali metal atom.
wherein E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R830R830R83- or -R83ZR83-, Z represents N-R83-A6 or N-A6, R79 to R83 individually represent a substituted or unsubstituted alkylene group, A2 to A6 individually represent a hydrogen atom, -OH, -COOM or -P03M2 and M is a hydrogen atom or an alkali metal atom.
6. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 5, wherein said compound represented by the formula (XII) or (XIII)
is a compound selected from the group consisting of:
(XII - 1) Ethylenediaminetetraacetic acid
(XII - 2) Diethylenetriaminepentaacetic acid
(XII - 4) Propylenediaminetetraacetic acid
(XII - 5) Triethylenetetraminehexaacetic acid
(XII - 7) 1,2-Diaminopropanetetraacetic acid
(XII - 8) 1,3-Diaminopropan-2-ol-tetraacetic acid
(XII - 19) Ethylenediaminetetramethylene phosphonic acid
(XIII - 1) Nitrilotriacetic acid
(XIII - 3) Hydroxyethyliminodiacetic acid
(XIII - 5) Nitrilotrimethylene phosphonic acid
7. The method for processing a light-sensitive silver halide color photographic material
as claimed in any of claims 1 to 6 wherein an amount of the bleaching solution to
be replenished is 40 mℓ to 250 mℓ per 1 m2 of the light-sensitive silver halide color photographic material.
8. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 7, wherein an amount of the bleaching solution to be replenished
is 50 mℓ to 200 mℓ per 1 m2 of the light-sensitive silver halide color photographic material.
9. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 2, wherein the bleaching solution contains at least one selected
from the group consisting of the compounds represented by the formulae (II), (III),
(V) or (VII).
10. The method for processing a light-sensitive silver halide color photographic material
as claimed in any of claims 1 to 9 wherein a color developing solution used for the
color development step contains a color developing agent represented by the following
formula (X):
wherein 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; R14 and R15 individually represent a hydrogen atom, an alkyl group or an aryl group, said alkyl or aryl group being optionally substituted; at least one of R14 and R15 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 or
said alkyl group being optionally further substituted; R16 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.
wherein 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; R14 and R15 individually represent a hydrogen atom, an alkyl group or an aryl group, said alkyl or aryl group being optionally substituted; at least one of R14 and R15 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 or
said alkyl group being optionally further substituted; R16 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.
11. The method for processing a light-sensitive silver halide color photographic material
as claimed in any of claims 1 to 10 wherein the light-sensitive silver halide photographic
material contains at least one of the compounds having the following general formula
(XI):
wherein Z11 and Z21 individually represent atom groups required for forming a benzene or naphthalene ring condensed to an oxazole ring; R41 and R42 individually represent an alkyl group, an alkenyl group, or an aryl group, R43 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X1⊖ represents an anion, and n is 1 or 0.
wherein Z11 and Z21 individually represent atom groups required for forming a benzene or naphthalene ring condensed to an oxazole ring; R41 and R42 individually represent an alkyl group, an alkenyl group, or an aryl group, R43 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X1⊖ represents an anion, and n is 1 or 0.
Claims for the following Contracting State(s) : GB
1. 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 developing agent; and R represents a hydrogen atom or a substituent; that the organic acid is contained in a range of not more than 10 mole % of the content of said organic acid ferric complex contained in said bleaching solution; and that the replenished amount in said bleaching step is 30 mî to 300 mî per 1m2 of said silver halide color photographic material, with the proviso that the magenta coupler of formula
is excepted from the magenta couplers of 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 developing agent; and R represents a hydrogen atom or a substituent; that the organic acid is contained in a range of not more than 10 mole % of the content of said organic acid ferric complex contained in said bleaching solution; and that the replenished amount in said bleaching step is 30 mî to 300 mî per 1m2 of said silver halide color photographic material, with the proviso that the magenta coupler of formula
is excepted from the magenta couplers of the general formula (M).
2. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 1, wherein said bleaching solution contains at least one of the
compounds having the under-mentioned general formulae (I) to (IX);
wherein 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,
wherein R2 and R3 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; A represents:
or an n1 -valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6- membered ring); X represents = S, = 0 or = NR"; R and R' each have the same meaning as defined for R2 and R3; X' has the same meaning as defined for X; Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, an alkyl group or
M represents a divalent metallic atom; R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring) or an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6; B represents an alkylene group having 1 to 6 carbon atoms; Y represents -N or -CH〈 ; R4 and R5 each have the same meaning as defined for R2 and R3; provided that R4 and R5 each may represent -B-SZ and that R2 and R3, R and R', and R4 and R5 each may be combined to form a ring,
wherein R6 and R7 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 -B1-S-Z1; provided that R6 and R7 may be combined to form a ring; Y1 represents N- or CH-; B1 represents an alkylene group having 1 to 6 carbon atoms; Z1 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,
wherein R8 and R9 each represent
; and R10 represents an alkyl group or -(CH2)n8SO3⊖ (provided that ℓ represents 0 when R10 is -(CH2)-n8SO3⊖, or 1 when it is an alkyl group); G⊖ represents an anion; and n8 represents an integer of 1 to 6,
wherein Q1 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 R11 represents a hydrogen atom, an alkali metal atom,
or an alkyl group; provided that Q' have the same meaning as defined for Qi,
wherein Di, D2, D3 and D4 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, said 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;
wherein X2 represents -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2 R16, -SO2 R16, -OR16, -NR16R17, -SR16, -SO3R16, -NHCOR16, -NHSO2R16, -OCOR16 or -SO2 R16; Y2 represents
or a hydrogen atom; and m9 and n9 each represent an integer of 1 to 10; R11, R12, R13, R14, R15, R17 and R18 each represent a hydrogen atom, a lower alkyl group, an acyl group or
wherein 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,
wherein R2 and R3 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; A represents:
or an n1 -valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6- membered ring); X represents = S, = 0 or = NR"; R and R' each have the same meaning as defined for R2 and R3; X' has the same meaning as defined for X; Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, an alkyl group or
M represents a divalent metallic atom; R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring) or an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6; B represents an alkylene group having 1 to 6 carbon atoms; Y represents -N or -CH〈 ; R4 and R5 each have the same meaning as defined for R2 and R3; provided that R4 and R5 each may represent -B-SZ and that R2 and R3, R and R', and R4 and R5 each may be combined to form a ring,
wherein R6 and R7 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 -B1-S-Z1; provided that R6 and R7 may be combined to form a ring; Y1 represents N- or CH-; B1 represents an alkylene group having 1 to 6 carbon atoms; Z1 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,
wherein R8 and R9 each represent
; and R10 represents an alkyl group or -(CH2)n8SO3⊖ (provided that ℓ represents 0 when R10 is -(CH2)-n8SO3⊖, or 1 when it is an alkyl group); G⊖ represents an anion; and n8 represents an integer of 1 to 6,
wherein Q1 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 R11 represents a hydrogen atom, an alkali metal atom,
or an alkyl group; provided that Q' have the same meaning as defined for Qi,
wherein Di, D2, D3 and D4 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, said 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;
wherein X2 represents -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2 R16, -SO2 R16, -OR16, -NR16R17, -SR16, -SO3R16, -NHCOR16, -NHSO2R16, -OCOR16 or -SO2 R16; Y2 represents
or a hydrogen atom; and m9 and n9 each represent an integer of 1 to 10; R11, R12, R13, R14, R15, R17 and R18 each represent a hydrogen atom, a lower alkyl group, an acyl group or
R16 represents a lower alkyl group;
R19 represents -NR20R21, -OR22 or -SR22; R20 and R21 each represent a hydrogen atom or a lower alkyl group; and R22 represents a group of atoms necessary for a ring to be formed by combination with
R18; R20 or R11 may be combined with R18 to form a ring; M' represents a hydrogen atom or a cation,
wherein 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; B2 and B3 each represent a lower alkylene group; R23, R24, R25 and R26 each represent a hydroxyl substituted lower alkyl group; and x and y each represent
0 or 1; G' represents an anion; and z represents 0, 1 or 2,
wherein R29 and R30 each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
R3, represents a hydrogen atom or an alkyl group; R32 represents a hydrogen atom or a carboxyl group.
3. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 1 or 2 wherein at least one layer of said light-sensitive silver
halide color photographic material contains a cyan coupler having the general formula
(C):
wherein R2, represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R24 represents an unsubstituted or substituted aryl group; and Z represents a hydrogen atom or a group iliminatable through coupling reaction with an oxidizing product of a N-hydroxyalkyl substituted-p-phenylenediamine derivative developing agent.
wherein R2, represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R24 represents an unsubstituted or substituted aryl group; and Z represents a hydrogen atom or a group iliminatable through coupling reaction with an oxidizing product of a N-hydroxyalkyl substituted-p-phenylenediamine derivative developing agent.
4. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 1, 2 or 3, wherein at least one of the substituents in general
formula (M) represents an aromatic sulfonyl group represented by the following formula
(A)
wherein R represents an aliphatic group, an aryl group or a heterocyclic group; m represents an integer of 1 or 2, R1 may be identical or different when m is 2; R2 represents an aliphatic group, an aryl group, a heterocyclic group or
where R3 and R4 each represent a hydrogen atom, an aliphatic group or an aryl group.
wherein R represents an aliphatic group, an aryl group or a heterocyclic group; m represents an integer of 1 or 2, R1 may be identical or different when m is 2; R2 represents an aliphatic group, an aryl group, a heterocyclic group or
where R3 and R4 each represent a hydrogen atom, an aliphatic group or an aryl group.
5. The method for processing a light-sensitive silver halide color photographic material
as claimed in any of claims 1 to 4, wherein the organic acid or organic acid capable
of forming the organic acid ferric complex is a compound represented by the following
general formulae (XII) or (XIII):
wherein E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R830R830R83- or -R83ZR83-, Z represents N-R83-A6 or N-A6, R79 to R83 individually represent a substituted or unsubstituted alkylene group, A2 to A6 individually represent a hydrogen atom, -OH, -COOM or -P03M2 and M is a hydrogen atom or an alkali metal atom.
wherein E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R830R830R83- or -R83ZR83-, Z represents N-R83-A6 or N-A6, R79 to R83 individually represent a substituted or unsubstituted alkylene group, A2 to A6 individually represent a hydrogen atom, -OH, -COOM or -P03M2 and M is a hydrogen atom or an alkali metal atom.
6. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 5, wherein said compound represented by the formula (XII) or (XIII)
is a compound selected from the group consisting of:
(XII - 1) Ethylenediaminetetraacetic acid
(XII - 2) Diethylenetriaminepentaacetic acid
(XII - 4) Propylenediaminetetraacetic acid
(XII - 5) Triethylenetetraminehexaacetic acid
(XII - 7) 1,2-Diaminopropanetetraacetic acid
(XII - 8) 1,3-Diaminopropan-2-ol-tetraacetic acid
(XII - 19) Ethylenediaminetetramethylene phosphonic acid
(XIII - 1) Nitrilotriacetic acid
(XIII - 3) Hydroxyethyliminodiacetic acid
(XIII - 5) Nitrilotrimethylene phosphonic acid
7. The method for processing a light-sensitive silver halide color photographic material
as claimed in any of claims 1 to 6 wherein an amount of the bleaching solution to
be replenished is 40 mî to 250 mℓ per 1 m2 of the light-sensitive silver halide color photographic material.
8. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 7, wherein an amount of the bleaching solution to be replenished
is 50 mℓ to 200 mℓ per 1 m2 of the light-sensitive silver halide color photographic material.
9. The method for processing a light-sensitive silver halide color photographic material
as claimed in claim 2, wherein the bleaching solution contains at least one selected
from the group consisting of the compounds represented by the formulae (II), (III),
(V) or (VII).
10. The method for processing a light-sensitive silver halide color photographic material
as claimed in any of claims 1 to 9 wherein a color developing solution used for the
color development step contains a color developing agent represented by the following
formula (X):
wherein R13 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; R14 and R15 individually represent a hydrogen atom, an alkyl group or an aryl group, said alkyl or aryl group being optionally substituted; at least one of R14 and R15 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 or
said alkyl group being optionally further substituted; R16 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.
wherein R13 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; R14 and R15 individually represent a hydrogen atom, an alkyl group or an aryl group, said alkyl or aryl group being optionally substituted; at least one of R14 and R15 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 or
said alkyl group being optionally further substituted; R16 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.
11. The method for processing a light-sensitive silver halide color photographic material
as claimed in any of claims 1 to 10 wherein the light-sensitive silver halide photographic
material contains at least one of the compounds having the following general formula
(XI):
wherein Z11 and Z21 individually represent atom groups required for forming a benzene or naphthalene ring condensed to an oxazole ring; R41 and R42 individually represent an alkyl group, an alkenyl group, or an aryl group, R43 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X, represents an anion, and n is 1 or 0.
wherein Z11 and Z21 individually represent atom groups required for forming a benzene or naphthalene ring condensed to an oxazole ring; R41 and R42 individually represent an alkyl group, an alkenyl group, or an aryl group, R43 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X, represents an anion, and n is 1 or 0.
Patentansprüche für folgende(n) Vertragsstaat(en) : DE
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
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.
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;
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,
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
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
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,
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
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
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;
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
und n 7 ist eine ganze Zahl von 1 bis 6;
worin R8 und R9 jeweils darstellen
; 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;
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,
oder eine Alkylgruppe; mit der Maßgabe, daß Q' die gleiche Bedeutung wie für Q1 definiert hat;
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;
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
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
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,
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,
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:
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.
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)
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
wenn R3 und R4 jeweils ein Wasserstoffatom, eine aliphatische Gruppe oder eine Arylgruppe darstellen.
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
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:
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.
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:
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.
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:
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.
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.
Patentansprüche für folgende(n) Vertragsstaat(en) : GB
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
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, mit der Maßgabe, daß der Magenta-Kuppler der Formel
von den Magenta-Kupplern der allgemeinen Formel (M) ausgenommen ist.
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, mit der Maßgabe, daß der Magenta-Kuppler der Formel
von den Magenta-Kupplern der allgemeinen Formel (M) ausgenommen ist.
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;
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,
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
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
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,
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
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
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; allgemeine Formel (III):
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
und n 7 ist eine ganze Zahl von 1 bis 6;
worin R8 und R9 jeweils darstellen
; 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;
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,
oder eine Alkylgruppe; mit der Maßgabe, daß Q' die gleiche Bedeutung wie für Q1 definiert hat;
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;
worin X2 darstellt -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -C02R16, -SO2R16, -OR16, -NR16R17, -SR16, -SO3 R16, -NHCOR16, -NHSO2R16, -OCOR16 oder -SO2 R16; Y2 bedeutet
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
R16 ist eine niedere Alkylgruppe; R19 stellt dar -NR20R21, -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,
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,
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:
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.
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)
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
wenn R3 und R4 jeweils ein Wasserstoffatom, eine aliphatische Gruppe oder eine Arylgruppe darstellen.
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
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:
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.
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), (III), (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:
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.
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:
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.
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.
Revendications pour l'(les) Etat(s) contractant(s) suivant(s) : suivant : DE
1. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible présentant au moins une couche d'émulsion d'halogénure d'argent qui
comprend d'exposer à la lumière pour former une image et ensuite de traiter ce qui
comprend au moins une étape de traitement chromogène et une étape de blanchiment dans
laquelle une solution de blanchiment utilisée lors de ladite étape de blanchiment
contient au moins un complexe organique ferrique acide; et ladite solution de blanchiment
contient au moins un acide organique et ladite solution de blanchiment est régénérée,
caractérisé en ce qu'on traite un matériau photographique couleur d'halogénure d'argent
photosensible, dans lequel au moins une couche de ladite émulsion d'halogénure d'argent
contient au moins un coupleur magenta ayant la formule générale (M) :
dans laquelle Z représente un groupe d'atomes non métalliques nécessaire pour former un cycle hétérocyclique contenant de l'azote, ledit cycle ayant en variante un substituant; X représente un atome d'hydrogène ou un substituant éliminable par réaction avec un produit oxydé d'un agent développeur de couleur; et R représente un atome d'hydrogène ou un substituant; l'acide organique est compris dans un intervalle qui ne dépasse pas 10 % molaire de la teneur dudit complexe ferrique organique acide présent dans ladite solution de blanchiment, la quantité de régénérant à ladite étape de blanchiment est de 30 ml à 300 ml pour 1 m2 de matériau photographique couleur d'halogénure d'argent.
dans laquelle Z représente un groupe d'atomes non métalliques nécessaire pour former un cycle hétérocyclique contenant de l'azote, ledit cycle ayant en variante un substituant; X représente un atome d'hydrogène ou un substituant éliminable par réaction avec un produit oxydé d'un agent développeur de couleur; et R représente un atome d'hydrogène ou un substituant; l'acide organique est compris dans un intervalle qui ne dépasse pas 10 % molaire de la teneur dudit complexe ferrique organique acide présent dans ladite solution de blanchiment, la quantité de régénérant à ladite étape de blanchiment est de 30 ml à 300 ml pour 1 m2 de matériau photographique couleur d'halogénure d'argent.
2. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 1, dans lequel ladite solution de blanchiment
contient au moins l'un des composés ayant les formules générales mentionnées ci-dessous
(I) à (IX):
dans laquelle Q représente un groupe d'atomes nécessaires à la formation d'un cycle hétérocyclique contenant de l'azote (y compris le cycle condensé avec un cycle insaturé de 5 à 6 membres); et R représente un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle, un groupe aryle, un cycle hétérocyclique (y compris le cycle condensé avec un cycle insaturé de 5 à 6 membres) ou un groupe amino,
dans laquelle R2 et R3 représentent chacun un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle ayant de 1 à 3 atomes de carbone, un groupe aryle ou un groupe alcényle; A représente
ou un groupe résiduel hétérocyclique ni -valent (y compris le groupe condensé avec un cycle insaturé de 5 à 6 membres); X représente = S, = 0 ou = NR"; R et R' ont chacun la même signification que celle définie pour R2 et R3; X' a la même signification que celle définie pour X; Z représente un atome d'hydrogène, un atome de métal alcalin, un groupe ammonium, un groupe amino, un groupe résiduel hétérocyclique contenant de l'azote, un groupe alkyle ou
M représente un atome métallique divalent; R" représente un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle, un groupe aryle, un groupe résiduel hétérocyclique (y compris le groupe condensé avec un cycle insaturé de 5 ou 6 membres) ou un groupe amino; et n1 à n6 et m1 à m6 représentent chacun un entier de 1 à 6; B représente un groupe alkylène ayant de 1 à 6 atomes de carbone; Y représente -N 〈 ou -CH〈 ; R4 et R5 ont chacun la même signification que celle définie pour R2 et R3; à la condition que R4 et R5 puissent représenter chacun -B-SZ et que R2 et R3, R et R', et R4 et R5 puissent être combinés chacun pour former un cycle,
dans laquelle R6 et R7 représentent chacun un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle ayant 1 à 3 atomes de carbone, un groupe aryle, un groupe alcényle ou -B1-S-Z1 ; à la condition que R6 et R7 puissent être combinés pour former un cycle; Y1 représente N- ou CH-; B1 représente un groupe alkylène ayant de 1 à 6 atomes de carbone; Z1 représente un atome d'hydrogène, un atome de métal alcalin, un groupe ammonium, un groupe amino, un groupe résiduel hétérocyclique contenant de l'azote ou
et n7 représente un entier de 1 à 6,
dans laquelle R8 et R9 représentent chacun
ou
; et R10 représente un groupe alkyle ou -(CH2 )n8SO3⊖ (à condition que ℓ représente 0 quand R10 est -(CH2)n8SO3⊖ , ou 1 quand c'est un groupe alkyle); G⊖ représente un anion; et n8 représente un entier de 1 à 6,
dans laquelle Q1 représente un groupe d'atomes nécessaire à la formation d'un cycle hétérocyclique contenant de l'azote (y compris le cycle condensé avec un cycle insaturé ou saturé de 5 à 6 membres); et R11 représente un atome d'hydrogène, un atome de métal alcalin,
ou un groupe alkyle; à la condition que Q' ait la même signification que celle définie pour Qi,
dans laquelle Di, D2, D3 et D4 représentent chacun une simple liaison, un groupe alkylène ayant de 1 à 8 atomes de carbone ou un groupe vinylène; et q1, q2, q3 et q4 représentent chacun un entier 0, 1 ou 2, ledit cycle formé avec un atome de soufre, peut être encore condensé avec un cycle saturé ou non de 5 à 6 membres, à l'exception du soufre élémentaire;
dans laquelle X2 représente -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2 R16, -SO2 R16, -OR16, -NR16R17, -SR16, -SO3 R16, -NHCOR16, -NHSO2 R16, -OCOR16 ou -SO2 R16; Y2 représente
ou un atome d'hydrogène; et m9 et n9 représentent chacun un entier de 1 à 10; R11, R12, R13, R14, R15, R17 et R18 représentent chacun un atome d'hydrogène, un groupe alkyle inférieur, un groupe acyle ou
dans laquelle Q représente un groupe d'atomes nécessaires à la formation d'un cycle hétérocyclique contenant de l'azote (y compris le cycle condensé avec un cycle insaturé de 5 à 6 membres); et R représente un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle, un groupe aryle, un cycle hétérocyclique (y compris le cycle condensé avec un cycle insaturé de 5 à 6 membres) ou un groupe amino,
dans laquelle R2 et R3 représentent chacun un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle ayant de 1 à 3 atomes de carbone, un groupe aryle ou un groupe alcényle; A représente
ou un groupe résiduel hétérocyclique ni -valent (y compris le groupe condensé avec un cycle insaturé de 5 à 6 membres); X représente = S, = 0 ou = NR"; R et R' ont chacun la même signification que celle définie pour R2 et R3; X' a la même signification que celle définie pour X; Z représente un atome d'hydrogène, un atome de métal alcalin, un groupe ammonium, un groupe amino, un groupe résiduel hétérocyclique contenant de l'azote, un groupe alkyle ou
M représente un atome métallique divalent; R" représente un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle, un groupe aryle, un groupe résiduel hétérocyclique (y compris le groupe condensé avec un cycle insaturé de 5 ou 6 membres) ou un groupe amino; et n1 à n6 et m1 à m6 représentent chacun un entier de 1 à 6; B représente un groupe alkylène ayant de 1 à 6 atomes de carbone; Y représente -N 〈 ou -CH〈 ; R4 et R5 ont chacun la même signification que celle définie pour R2 et R3; à la condition que R4 et R5 puissent représenter chacun -B-SZ et que R2 et R3, R et R', et R4 et R5 puissent être combinés chacun pour former un cycle,
dans laquelle R6 et R7 représentent chacun un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle ayant 1 à 3 atomes de carbone, un groupe aryle, un groupe alcényle ou -B1-S-Z1 ; à la condition que R6 et R7 puissent être combinés pour former un cycle; Y1 représente N- ou CH-; B1 représente un groupe alkylène ayant de 1 à 6 atomes de carbone; Z1 représente un atome d'hydrogène, un atome de métal alcalin, un groupe ammonium, un groupe amino, un groupe résiduel hétérocyclique contenant de l'azote ou
et n7 représente un entier de 1 à 6,
dans laquelle R8 et R9 représentent chacun
ou
; et R10 représente un groupe alkyle ou -(CH2 )n8SO3⊖ (à condition que ℓ représente 0 quand R10 est -(CH2)n8SO3⊖ , ou 1 quand c'est un groupe alkyle); G⊖ représente un anion; et n8 représente un entier de 1 à 6,
dans laquelle Q1 représente un groupe d'atomes nécessaire à la formation d'un cycle hétérocyclique contenant de l'azote (y compris le cycle condensé avec un cycle insaturé ou saturé de 5 à 6 membres); et R11 représente un atome d'hydrogène, un atome de métal alcalin,
ou un groupe alkyle; à la condition que Q' ait la même signification que celle définie pour Qi,
dans laquelle Di, D2, D3 et D4 représentent chacun une simple liaison, un groupe alkylène ayant de 1 à 8 atomes de carbone ou un groupe vinylène; et q1, q2, q3 et q4 représentent chacun un entier 0, 1 ou 2, ledit cycle formé avec un atome de soufre, peut être encore condensé avec un cycle saturé ou non de 5 à 6 membres, à l'exception du soufre élémentaire;
dans laquelle X2 représente -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2 R16, -SO2 R16, -OR16, -NR16R17, -SR16, -SO3 R16, -NHCOR16, -NHSO2 R16, -OCOR16 ou -SO2 R16; Y2 représente
ou un atome d'hydrogène; et m9 et n9 représentent chacun un entier de 1 à 10; R11, R12, R13, R14, R15, R17 et R18 représentent chacun un atome d'hydrogène, un groupe alkyle inférieur, un groupe acyle ou
R16 représente un groupe alkyle inférieur;
R19 représente -NR20R21, -OR22 ou -SR22; R20 et R2, représentent chacun un atome d'hydrogène ou un groupe alkyle inférieur; et R22 représente un groupe d'atomes nécessaire pour former un cycle en combinaison avec
R18; R20 ou R11 peuvent être combinés avec R18 pour former un cycle; M' représente un atome d'hydrogène ou un cation,
dans laquelle Ar représente un groupe aryle divalent ou un groupe organique divalent
formé par combinaison d'un groupe aryle avec un atome d'oxygène et/ou un groupe alkylène;
B2 et B3 représentent chacun un groupe alkylène inférieur, R23, R24, R25 et R26 représentent chacun un groupe alkyle inférieur substitué par un hydroxyle; et x et
y représentent chacun 0 ou 1; G' représente un anion; et Z représente 0, 1 ou 2,
dans laquelle R29 et R30 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle ou un
groupe hétérocyclique; R3, représente un atome d'hydrogène ou un groupe alkyle; R32 représente un atome d'hydrogène ou un groupe carboxyle.
3. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 1 ou 2, dans lequel au moins une couche dudit
matériau photographique couleur d'halogénure d'argent photosensible contient un coupleur
cyan de formule générale (C) :
dans laquelle R21 représente un groupe alkyle, un groupe alcényle, un groupe cycloalkyle, un groupe aryle ou un groupe hétérocyclique; R24 représente un groupe aryle non substitué ou substitué; et Z représente un atome d'hydrogène ou un groupe éliminable par réaction de couplage avec un produit oxydant d'un agent développeur dérivé de p-phénylènediamine N-hydroxyalkyle substitué.
dans laquelle R21 représente un groupe alkyle, un groupe alcényle, un groupe cycloalkyle, un groupe aryle ou un groupe hétérocyclique; R24 représente un groupe aryle non substitué ou substitué; et Z représente un atome d'hydrogène ou un groupe éliminable par réaction de couplage avec un produit oxydant d'un agent développeur dérivé de p-phénylènediamine N-hydroxyalkyle substitué.
4. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 1, 2 ou 3, dans lequel au moins l'un des substituants
dans formule générale (M) représente un groupe sulfonyle aromatique, représenté par
la formule suivante (A)
dans laquelle R représente un groupe aliphatique, un groupe aryle ou un groupe hétérocyclique; m représente un entier 1 ou 2, R peut être identique ou différent quand m est 2; R2 représente un groupe aliphatique, un groupe aryle, un groupe hétérocyclique ou
où R3 et R4 représentent chacun un atome d'hydrogène, un groupe aliphatique ou un groupe aryle.
dans laquelle R représente un groupe aliphatique, un groupe aryle ou un groupe hétérocyclique; m représente un entier 1 ou 2, R peut être identique ou différent quand m est 2; R2 représente un groupe aliphatique, un groupe aryle, un groupe hétérocyclique ou
où R3 et R4 représentent chacun un atome d'hydrogène, un groupe aliphatique ou un groupe aryle.
5. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon l'une quelconque des revendications 1 à 4, dans lequel l'acide
organique ou l'acide organique capable de former le complexe ferrique organique acide
est un composé représenté par les formules générales suivantes (XII) ou (XIII) :
dans lesquelles E représente un groupe alkylène substitué ou non substitué, un groupe cycloalkylène, un groupe phénylène, -R830R830R83- ou R83ZR83-, Z représente N-R83-A6 ou N-A6, R79 à R83 individuellement représentent un groupe alkylène substitué ou non substitué, A2 à A6 représentent individuellement un atome d'hydrogène, -OH, -COOM ou PO3M2 et M est un atome d'hydrogène ou un atome de métal alcalin.
dans lesquelles E représente un groupe alkylène substitué ou non substitué, un groupe cycloalkylène, un groupe phénylène, -R830R830R83- ou R83ZR83-, Z représente N-R83-A6 ou N-A6, R79 à R83 individuellement représentent un groupe alkylène substitué ou non substitué, A2 à A6 représentent individuellement un atome d'hydrogène, -OH, -COOM ou PO3M2 et M est un atome d'hydrogène ou un atome de métal alcalin.
6. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 5, dans lequel ledit composé représenté par la
formule (XII) ou (XIII) est un composé choisi dans le groupe constitué de :
(XII - 1) acide éthylènediaminetétraacétique
(XII - 2) acide diéthylènetriaminepentaacétique
(XII - 4) acide propylènediaminetétraacétique
(XII - 5) acide triéthylènetétraminehexaacétique
(XII - 7) acide 1,2-diaminopropanetétraacétique
(XII - 8) acide 1,3-diaminopropane-2-ol-tétraacétique
(XII - 19) acide éthylènediaminetétraméthylène phosphonique
(XIII - 1) acide nitrilotriacétique
(XIII - 3) acide hydroxyéthyliminodiacétique
(XIII - 5) acide nitrilotriméthylène phosphonique
7. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon l'une quelconque des revendications 1 à 6, dans laquelle la quantité
de solution de blanchiment à régénérer est de 40 ml à 250 ml par 1 m2 de matériau photographique couleur d'halogénure d'argent photosensible.
8. Procédé de traitement de matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 7, dans lequel la quantité de solution de blanchiment
à régénérer est de 50 ml à 200 ml par 1 m2 de matériau photographique couleur d'halogénure d'argent photosensible.
9. Procédé de traitement de matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 2 dans lequel la solution de blanchiment contient
au moins l'un des composés choisi dans le groupe constitué des composés représentés
par les formules (II), (III), (V) ou (VII).
10. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon l'une quelconque des revendications 1 à 9, dans lequel on utilise
une solution révélatrice de couleur à l'étape du développement de la couleur qui contient
un agent développeur de couleur représenté par la formule suivante (X) :
dans laquelle R représente un atome d'hydrogène, un atome d'halogène, ou un groupe alkyle, ledit groupe alkyle ayant une chaîne droite ou ramifiée de 1 à 5 atomes de carbone et en option un substituant R14 et R15 représentent individuellement un atome d'hydrogène, un groupe alkyle ou un groupe aryle, ledit groupe alkyle ou aryle étant substitué en variante; au moins l'un des groupes R14 et R15 est un groupe alkyle substitué par un groupe hydrosoluble, tel qu'un groupe hydroxy, un groupe carboxy, un groupe acide sulfonique, un groupe amino, un groupe sulfonamido ou
ledit groupe alkyle étant encore substitué en variante; R16 représente un atome d'hydrogène ou un groupe alkyle ayant une chaîne droite ou ramifiée de 1 à 5 atomes de carbone et p et q représentent chacun un entier de 1 à 5.
dans laquelle R représente un atome d'hydrogène, un atome d'halogène, ou un groupe alkyle, ledit groupe alkyle ayant une chaîne droite ou ramifiée de 1 à 5 atomes de carbone et en option un substituant R14 et R15 représentent individuellement un atome d'hydrogène, un groupe alkyle ou un groupe aryle, ledit groupe alkyle ou aryle étant substitué en variante; au moins l'un des groupes R14 et R15 est un groupe alkyle substitué par un groupe hydrosoluble, tel qu'un groupe hydroxy, un groupe carboxy, un groupe acide sulfonique, un groupe amino, un groupe sulfonamido ou
ledit groupe alkyle étant encore substitué en variante; R16 représente un atome d'hydrogène ou un groupe alkyle ayant une chaîne droite ou ramifiée de 1 à 5 atomes de carbone et p et q représentent chacun un entier de 1 à 5.
11. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon l'une quelconque des revendications 1 à 10 dans lequel le matériau
photographique d'halogénure d'argent photosensible contient au moins l'un des composés
ayant la formule générale (XI) :
dans laquelle Z11 et Z2, représentent individuellement des groupes d'atomes requis pour former un cycle benzénique ou naphtalénique condensés sur un cycle oxazole; R41 et R42 représentent individuellement un groupe alkyle, un groupe alcényle ou un groupe aryle, R43 représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 3 atomes de carbone, X, représente un anion et n est 1 ou 0.
dans laquelle Z11 et Z2, représentent individuellement des groupes d'atomes requis pour former un cycle benzénique ou naphtalénique condensés sur un cycle oxazole; R41 et R42 représentent individuellement un groupe alkyle, un groupe alcényle ou un groupe aryle, R43 représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 3 atomes de carbone, X, représente un anion et n est 1 ou 0.
Revendications pour l'(les) Etat(s) contractant(s) suivant(s) : suivant : GB
1. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible présentant au moins une couche d'émulsion d'halogéure d'argent qui comprend
d'exposer à la lumière pour former une image et ensuite de traiter ce qui comprend
au moins une étape de traitement chromogène et une étape de blanchiment dans laquelle
une solution de blanchiment utilisée lors de ladite étape de blanchiment contient
au moins un complexe organique ferrique acide; et ladite solution de blanchiment contient
au moins un acide organique et ladite solution de blanchiment est régénérée, caractérisé
en ce qu'on traite un matériau photographique couleur d'halogénure d'argent photosensible,
dans lequel au moins une couche de ladite émulsion d'halogénure d'argent contient
au moins un coupleur magenta ayant la formule générale (M) :
dans laquelle Z représente un groupe d'atomes non métalliques nécessaire pour former un cycle hétérocyclique contenant de l'azote, ledit cycle ayant en variante un substituant; X représente un atome d'hydrogène ou un substituant éliminable par réaction avec un produit oxydé d'un agent développeur de couleur; et R représente un atome d'hydrogène ou un substituant; l'acide organique est compris dans un intervalle qui ne dépasse pas 10 % molaire de la teneur dudit complexe ferrique organique acide présent dans ladite solution de blanchiment , la quantité de régénérant à ladite étape de blanchiment est de 30 ml à 300 ml pour 1 m2 de matériau photographique couleur d'halogénure d'argent, à la condition que le coupleur magenta de formule
soit exclu des coupleurs magenta de formule générale M.
dans laquelle Z représente un groupe d'atomes non métalliques nécessaire pour former un cycle hétérocyclique contenant de l'azote, ledit cycle ayant en variante un substituant; X représente un atome d'hydrogène ou un substituant éliminable par réaction avec un produit oxydé d'un agent développeur de couleur; et R représente un atome d'hydrogène ou un substituant; l'acide organique est compris dans un intervalle qui ne dépasse pas 10 % molaire de la teneur dudit complexe ferrique organique acide présent dans ladite solution de blanchiment , la quantité de régénérant à ladite étape de blanchiment est de 30 ml à 300 ml pour 1 m2 de matériau photographique couleur d'halogénure d'argent, à la condition que le coupleur magenta de formule
soit exclu des coupleurs magenta de formule générale M.
2. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 1, dans lequel ladite solution de blanchiment
contient au moins l'un des composés ayant les formules générales mentionnées ci-dessous
(I) à (IX);
dans laquelle R représente un groupe d'atomes nécessaires à la formation d'un cycle hétérocyclique contenant de l'azote (y compris le cycle condensé avec un cycle insaturé de 5 à 6 membres), et R représente un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle, un groupe aryle, un cycle hétérocyclique (y compris le cycle condensé avec un cycle insaturé de 5 à 6 membres) ou un groupe amino,
dans laquelle R2 et R3 représentent chacun un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle ayant de 1 à 3 atomes de carbone, un groupe aryle ou un groupe alcényle;
dans laquelle R représente un groupe d'atomes nécessaires à la formation d'un cycle hétérocyclique contenant de l'azote (y compris le cycle condensé avec un cycle insaturé de 5 à 6 membres), et R représente un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle, un groupe aryle, un cycle hétérocyclique (y compris le cycle condensé avec un cycle insaturé de 5 à 6 membres) ou un groupe amino,
dans laquelle R2 et R3 représentent chacun un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle ayant de 1 à 3 atomes de carbone, un groupe aryle ou un groupe alcényle;
A représente
ou un groupe résiduel hétérocyclique ni -valent (y compris le groupe condensé avec
un cycle insaturé de 5 à 6 membres); X représente = S, = 0 ou = NR"; R et R' ont chacun
la même signification que celle définie pour R2 et R3; X' a la même signification que celle définie pour X; Z représente un atome d'hydrogène,
un atome de métal alcalin, un groupe ammonium, un groupe amino, un groupe résiduel
hétérocyclique contenant de l'azote, un groupe alkyle ou
M représente un atome métallique divalent; R" représente un atome d'hydrogène, un
groupe alkyle ayant de 1 à 6 atomes de carbone, un groupe cycloalkyle, un groupe aryle,
un groupe résiduel hétérocyclique (y compris le groupe condensé avec un cycle insaturé
de 5 ou 6 membres) ou un groupe amino; et n1 à n6et m1 à m6 représentent chacun un entier de 1 à 6; B représente un groupe alkylène ayant de
1 à 6 atomes de carbone; Y représente -N 〈 ou -CH〈 ; R4 et R5 ont chacun la même signification que celle définie pour R2 et R3; à la condition que R4 et R5 puissent représenter chacun -B-SZ et que R2 et R3, R et R', et R4 et R5 puissent être combinés chacun pour former un cycle,
dans laquelle R6 et R7 représentent chacun un atome d'hydrogène, un groupe alkyle ayant de 1 à 6 atomes
de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle
ayant 1 à 3 atomes de carbone, un groupe aryle, un groupe alcényle ou -B1-S-Z1; à la condition que R6 et R7 puissent être combinés pour former un cycle; Y1 représente N ou CH-; B1 représente un groupe alkylène ayant de 1 à 6 atomes de carbone; Z1 représente un atome d'hydrogène, un atome de métal alcalin, un groupe ammonium, un
groupe amino, un groupe résiduel hétérocyclique contenant de l'azote ou
et n7 représente un entier de 1 à 6,
dans laquelle R8 et R9 représentent chacun
ou
; et R10 représente un groupe alkyle ou -(CH2)n8SO3⊖ (à condition que 1 représente 0 quand R10 est -(CH2)n8SO3⊖ , ou 1 quand c'est un groupe alkyle); G⊖ représente un anion; et n8 représente un
entier de 1 à 6,
dans laquelle Q1 représente un groupe d'atomes nécessaire à la formation d'un cycle hétérocyclique
contenant de l'azote ( y compris le cycle condensé avec un cycle insaturé ou saturé
de 5 à 6 membres); et R11 représente un atome d'hydrogène, un atome de métal alcalin,
ou un groupe alkyle; à la condition que Q' ait la même signification que celle définie
pour Q1,
dans laquelle Di, D2, D3 et D4 représentent chacun une simple liaison, un groupe alkylène ayant de 1 à 8 atomes
de carbone ou un groupe vinylène, et q1, q2, q3 et q4 représentent chacun un entier
0, 1 ou 2, ledit cycle formé avec un atome de soufre peut être encore condensé avec
un cycle saturé ou non de 5 à 6 membres, à l'exception du soufre élémentaire;
dans laquelle X2 représente -COOM', -OH, -SO3M', -CONH2, -S02NH2, -NH2, -SH, -CN, -CO2 R16, -SO2 R16, -OR16, -NR16R17, -SR16, -SO3 R16, -NHCOR16, -NHSO2 R16, -OCOR16 ou -SO2 R16; Y2 représente
ou un atome d'hydrogène; et m9 et n9 représentent chacun un entier de 1 à 10; R11, R12, R13, R14, R15, R17 et R18 représentent chacun un atome d'hydrogène, un groupe alkyle inférieur, un groupe acyle
ou
R16 représente un groupe alkyle inférieur;
R19 représente -NR20R21, -OR22 ou -SR22; R20 et R21 représentent chacun un atome d'hydrogène ou un groupe alkyle inférieur; et R22 représente un groupe d'atomes nécessaire pour former un cycle en combinaison avec
R18; R20 ou R11 peuvent être combinés avec R18 pour former un cycle; M' représente un atome d'hydrogène ou un cation,
dans laquelle Ar représente un groupe aryle divalent ou un groupe organique divalent
formé par combinaison d'un groupe aryle avec un atome d'oxygène et/ou un groupe alkylène;
B2 et B3 représentent chacun un groupe alkylène inférieur; R23, R24, R25 et R26 représentent chacun un groupe alkyle inférieur substitué par un hydroxyle; et x et
y représentent chacun 0 ou 1; G' représente un anion; et z représente 0, 1 ou 2,
dans laquelle R29 et R30 représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle ou un
groupe hétérocyclique; R3, représente un atome d'hydrogène ou un groupe alkyle; R32 représente un atome d'hydrogène ou un groupe carboxyle.
3. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 1 ou 2, dans lequel au moins une couche dudit
matériau photographique couleur d'halogénure d'argent photosensible contient un coupleur
cyan de formule générale (C) :
dans laquelle R2, représente un groupe alkyle, un groupe alcényle, un groupe cycloalkyle, un groupe aryle ou un groupe hétérocyclique; R24 représente un groupe aryle non substitué ou substitué; et Z représente un atome d'hydrogène ou un groupe éliminable par réaction de couplage avec un produit oxydant d'un agent développeur dérivé de p-phénylènediamine N-hydroxyalkyle substitué.
dans laquelle R2, représente un groupe alkyle, un groupe alcényle, un groupe cycloalkyle, un groupe aryle ou un groupe hétérocyclique; R24 représente un groupe aryle non substitué ou substitué; et Z représente un atome d'hydrogène ou un groupe éliminable par réaction de couplage avec un produit oxydant d'un agent développeur dérivé de p-phénylènediamine N-hydroxyalkyle substitué.
4. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 1, 2 ou 3, dans lequel au moins l'un des substituants
dans formule générale (M) représente un groupe sulfonyle aromatique, représenté par
la formule suivante (A) :
dans laquelle R représente un groupe aliphatique, un groupe aryle ou un groupe hétérocyclique; m représente un entier, 1 ou 2, R1 peut être identique ou différent quand m est 2; R2 représente un groupe aliphatique, un groupe aryle, un groupe hétérocyclique ou
où R3 et R4 représentent chacun un atome d'hydrogène, un groupe aliphatique ou un groupe aryle.
dans laquelle R représente un groupe aliphatique, un groupe aryle ou un groupe hétérocyclique; m représente un entier, 1 ou 2, R1 peut être identique ou différent quand m est 2; R2 représente un groupe aliphatique, un groupe aryle, un groupe hétérocyclique ou
où R3 et R4 représentent chacun un atome d'hydrogène, un groupe aliphatique ou un groupe aryle.
5. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon l'une quelconque des revendications 1 à 4, dans lequel l'acide
organique ou l'acide organique capable de former le complexe ferrique organique acide
est un composé représenté par les formules générales suivantes (XII) ou (XIII) :
dans lesquelles E représente un groupe alkylène substitué ou non substitué, un groupe cycloalkylène, un groupe phénylène, -R830R830R83- ou R83ZR83-, Z représente N-R83-A6 ou N-A6, R79 à R83 individuellement représentent un groupe alkylène substitué ou non substitué, A2 à A6 représentent individuellement un atome d'hydrogène, -OH, -COOM où PÛ3M2 et M est un atome d'hydrogène ou un atome de métal alcalin.
dans lesquelles E représente un groupe alkylène substitué ou non substitué, un groupe cycloalkylène, un groupe phénylène, -R830R830R83- ou R83ZR83-, Z représente N-R83-A6 ou N-A6, R79 à R83 individuellement représentent un groupe alkylène substitué ou non substitué, A2 à A6 représentent individuellement un atome d'hydrogène, -OH, -COOM où PÛ3M2 et M est un atome d'hydrogène ou un atome de métal alcalin.
6. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 5, dans lequel ledit composé représenté par la
formule (XII) ou (XIII) est un composé choisi dans le groupe constitué de :
(XII - 1) acide éthylènediaminetétraacétique
(XII - 2) acide diéthylènetriaminepentaacétique
(XII - 4) acide propylènediaminetétraacétique
(XII - 5) acide triéthylènetétraminehexaacétique
(XII - 7) acide 1,2-diaminopropanetétraacétique
(XII - 8) acide 1,3-diaminopropane-2-ol-tétraacétique
(XII - 19) acide éthylènediaminetétraméthylène phosphonique
(XIII - 1) acide nitrilotriacétique
(XIII - 3) acide hydroxyéthyliminodiacétique
(XIII - 5) acide nitrilotriméthylène phosphonique
7. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon l'une quelconque des revendications 1 à 6, dans laquelle la quantité
de solution de blanchiment à régénérer est de 40 ml à 250 ml par 1 m2 de matériau photographique couleur d'halogénure d'argent photosensible.
8. Procédé de traitement de matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 7, dans lequel la quantité de solution de blanchiment
à régénérer est de 50 ml à 200 ml par 1 m2 de matériau photographique couleur d'halogénure d'argent photosensible.
9. Procédé de traitement de matériau photographique couleur d'halogénure d'argent
photosensible selon la revendication 2 dans lequel la solution de blanchiment contient
au moins l'un des composés choisi dans le groupe constitué des composés représentés
par les formules (II), (III), (V) ou (VII).
10. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon l'une quelconque des revendications 1 à 9, dans lequel on utilise
une solution révélatrice de couleur à l'étape du développement de la couleur qui contient
un agent développeur de couleur représenté par la formule suivante (X) :
dans laquelle R13 représente un atome d'hydrogène, un atome d'halogène, ou un groupe alkyle, ledit groupe alkyle ayant une chaîne droite ou ramifiée de 1 à 5 atomes de carbone et en option un substituant, R14 et R15 représentent individuellement un atome d'hydrogène, un groupe alkyle ou un groupe aryle, ledit groupe alkyle ou aryle étant substitué en variante; au moins l'un des groupes R14 et R15 est un groupe alkyle substitué par un groupe hydrosoluble, tel qu'un groupe hydroxy, un groupe carboxy, un groupe acide sulfonique, un groupe amino, un groupe sulfonamido ou
ledit groupe alkyle étant encore substitué en variante; R16 représente un atome d'hydrogène ou un groupe alkyle ayant une chaîne droite ou ramifiée de 1 à 5 atomes de carbone et p et q représentent chacun un entier de 1 à 5.
dans laquelle R13 représente un atome d'hydrogène, un atome d'halogène, ou un groupe alkyle, ledit groupe alkyle ayant une chaîne droite ou ramifiée de 1 à 5 atomes de carbone et en option un substituant, R14 et R15 représentent individuellement un atome d'hydrogène, un groupe alkyle ou un groupe aryle, ledit groupe alkyle ou aryle étant substitué en variante; au moins l'un des groupes R14 et R15 est un groupe alkyle substitué par un groupe hydrosoluble, tel qu'un groupe hydroxy, un groupe carboxy, un groupe acide sulfonique, un groupe amino, un groupe sulfonamido ou
ledit groupe alkyle étant encore substitué en variante; R16 représente un atome d'hydrogène ou un groupe alkyle ayant une chaîne droite ou ramifiée de 1 à 5 atomes de carbone et p et q représentent chacun un entier de 1 à 5.
11. Procédé de traitement d'un matériau photographique couleur d'halogénure d'argent
photosensible selon l'une quelconque des revendications 1 à 10 dans lequel le matériau
photographique d'halogénure d'argent photosensible contient au moins l'un des composés
ayant la formule générale (XI) :
dans laquelle Z11 et Z2, représentent individuellement des groupes d'atomes requis pour former un cycle benzénique ou naphtalénique condensés sur un cycle oxazole; R41 et R42 représentent individuellement un groupe alkyle, un groupe alcényle ou un groupe aryle, R43 représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 3 atomes de carbone, X1⊖ représente un anion et n est 1 ou 0.
dans laquelle Z11 et Z2, représentent individuellement des groupes d'atomes requis pour former un cycle benzénique ou naphtalénique condensés sur un cycle oxazole; R41 et R42 représentent individuellement un groupe alkyle, un groupe alcényle ou un groupe aryle, R43 représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 3 atomes de carbone, X1⊖ représente un anion et n est 1 ou 0.