EP0243866A2

EP0243866A2 - Method for processing light-sensitive halide color photographic material

Info

Publication number: EP0243866A2
Application number: EP19870105906
Authority: EP
Inventors: Moeko Hagiwara Nee Higuchi; Shigeharu Koboshi; Satoru Kuse
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1986-04-23
Filing date: 1987-04-22
Publication date: 1987-11-04
Anticipated expiration: 2007-04-22
Also published as: DE3789249T2; EP0243866A3; DE3789249D1; EP0243866B1

Abstract

Disclosed is 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, the improvement 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 in a range of not more than 10 mole % of the content of said organic acid ferric complex contained in said bleaching solution; and a replenished amount in said bleaching step is 30 mf to 300 mℓ per 1m² of said silver halide color photographic material.

This invention can provide 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.

Description

This invention relates to a method for processing a light-sensitive silver halide color photographic material. More particularly, it is concerned with a method for processing a light-sensitive silver halide color photographic material without any impairment of recoloring property even if a replenished amount of a bleaching solution is reduced.
Processing of light-sensitive materials comprises basically two steps of color development and desilvering and the desilvering step comprises a breaching and fixing steps or a bleach-fixing step. Besides these steps, linse processing, stabilizing processing and so on may be added as additional processing steps.
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.
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.
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.
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 (ethylenediaminetetraacetato)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.
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.
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.
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.
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.
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.
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.
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.
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.
Another object of this invention is to provide a method for processing a light-sensitive silver halide color photographic material which shows an excellent silver bleaching efficacy and an improved production of leuco cyan dyes.
A still another object of this invention is to provide a method for processing a light-sensitive silver halide color photographic material with an improved generation of bleaching stain even in a condensed, low replenishing process.
A further object of this invention is to provide a method for processing a light-sensitive silver halide color photographic material with less complicated procedures and less control of processing solutions.
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, the improvement 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 in a range of not more than 10 mole % of the content of said organic acid ferric complex contained in said bleaching solution; and a replenished amount in said bleaching step is 30 ml to 300 ml per 1 m² of said light-sensitive silver halide color photographic material.
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.
General Formula (I):
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 R₁ 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.
General Formula (II):
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 n_l-valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring); X represents =S, =0 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 nl to n6 and ml to m5 each represent an integer of 1 to 6. B represents an alkylene group having 1 to 6 carbon atoms; Y represents
or
; R₄ and RS 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.
The compound represented by the above formula may also include an enol form compound and a salt thereof.
General Formula (III):
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.
General Formula (IV):
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.
General Formula (V):
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 Q₁·
General Formula (VI):
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 ql, 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.
General Formula (VII):
In the formula, X₂ represents -COOM', -OH, -SO₃M' , -CONH₂, -SO₂NH₂, -NH₂, -SH, -CN, -CO₂R₁₆, -SO₂R₁₆, -^OR ₁₆, NR₁₆R₁₇, -SR₁₆, -SO₃R₁₆, -^NH^COR₁₆, -NHSO₂R₁₆, -OCOR₁₆ or -SO₂R₁₆; Y₂ represents
or a hydrogen atom; and m9 and n9 each represent an integer of 1 to 10. R₁₁, ^R1_2f 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 -NR₂₀OR₂₁, -OR₂₂ or -SR₂₂; R₂₀ and ^R ₂₁ 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.
General Formula (VIII):
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.
General Formula (IX):
In the formula, R₂₉ and R₃₀ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; _R31 represents a hydrogen atom or an alkyl group; R₃₂ represents a hydrogen atom or a carboxyl group.
The compounds represented respectively by General Formulae (I) to (IX) preferably used in this invention are compounds generally used as bleach accelerators, which are hereinafter referred to as the bleach accelerators of this invention.
Typical examples of the bleach accelerators of this invention may include, for example, the following, but by no means limited to these.
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).
General Formula (C):
(wherein R₂₁ 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).
As other preferred emobidment of this invention, there is the emboidment wherein at least one layer of said silver halide emulsion layer contains at least one magenta coupler having the general formula (M):

Formura (M)-:
(wherein Z represents a non-metal atom group necessary to form a nitrogen-containing heterocyclic ring, said ring optionally having a substitutent; X represents a hydrogen atom or a substituent eliminatable through a reaction with an oxidized product of a color developing agent; and R represents a hydrogen atom or a substituent).

As further preferred embodiment of this invention, there is the embodiment wherein at least one layer of said silver halide emulsion layer contains at least one pyrazoloazol series magenta coupler having at least one aromatic sulfonyl group represented by the following formula in its molecular structure:

Formula (A)
wherein R_l 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
when R₃ and R₄ each represent a hydrogen atom, an aliphatic group or an aryl group.

[Detailed description of the invention]

This invention will be more fully illustrated hereinbelow.
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.
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.
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.
An amount of the present bleaching solution to be replenished is 30 ml to 300 mℓ per 1 m²of a light-sensitive silver halide color photographic material, more preferably 40 ml to 250 mℓ, most preferably 50 mℓ to 200 mℓ.
The organic acid or organic acid capable of forming the organic acid ferric complex may be suitably an aminocarboxylic acid compound or an amin acid compound, namely the amino compound having at least 2 or more carboxy groups or the amino compound having at least 2 or more phosphonic acid groups; preferably those compounds having the following general formulae (XII) and (XIII).
In the above formulae, E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R₈₃OR₈₃OR₈₃- 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 -PO₃M₂ and M is a hydrogen atom or an alkali metal atom. Preferable illustrated compounds having the general formula (XII) and (XIII) are given below.

Illustrated Compound

(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) l,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-(P-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

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).
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 cc-existing in a bleaching solution, preferably 0 to 5 %, more preferably 0 to 2 % for still more effective exertion of the present effects.
The ferric complex of organic acid according to this invention may be employed as a free acid (a hydroacid), an alkali metal salt such as sodium salt, potassium salt or lithium salt, an ammonium salt, a water-soluble amine salt such as triethanol amine salt, preferably potassium salt, sodium salt or ammonium salt. The ferric complexes may be employed with at least one sort thereof or in combination with 2 or more thereof. The amount to be used may be optionally selected and should be determined depending upon the silver amount of light-sensitive material to be processed, composition of a silver halide and the like; for instance, one may use not less than 0.01 mole per 1 litre of the solution employed, preferably 0.05 to 0.6 mole. And, it is preferred in a replenishing solution to employ a concentration of the solubility as condensed as possible for condensed, low replenishment.
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.
General Formula (I):
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 R₁ 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.
General Formula (II):
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 n_l-valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring); X represents =S, =0 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 nl to n6 and ml to m5 each represent an integer of 1 to 6. B represents an alkylene group having 1 to 6 carbon atoms; Y represents
or
and each have the same meaning as defined ; R4 and R₅ each have the same meaning as defined for _R2and _R3; provided that R 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.
The compound represented by the above formula may also include an enol form compound and a salt thereof.
General Formula (III):
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
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.
General Formula (IV):
In the formula, R₈ and R₉ each represent
or
; and R₁₀ represents an alkyl group or -(CH₂)_n8SO₃⊖ (provided that ℓ represents 0 when R ₀ is -(CH₂)_n8SO₃⊖, or 1 when it is an alkyl group). G⊖ represents an anion; and n8 represent an integer of 1 to 6.
General Formula (V):
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 Q₁.
General Formula (VI):
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 ql, 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.
General Formula (VII):
In the formula, X₂ represents -COOM', -OH, -SO₃M', -CONH₂, -SO₂NH₂, -NH₂, -^SH, -^CN, -CO₂R₁₆, -SO₂R₁₆, -OR₁₆, NR₁₆R₁₇, -SR₁₆, -SO₃R₁₆, -NHCOR₁₆, -NHSO₂R₁₆, -OCOR16 or -SO₂R₁₆; Y₂ represents
or a hydrogen atom; and m9 and n9 each represent an integer of 1 to 10. R₁₁, ^R _12' 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; B₂₀ 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.
General Formula (VIII):
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, R_24' ^R ₂₅ 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.
General Formula (IX):
In the formula, _R29 and _R30 each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R₃₁ represents a hydrogen atom or an alkyl groups R₃₂ represents a hydrogen atom or a carboxyl group.
The compounds represented respectively by General Formulae (I) to (IX) preferably used in this invention are compounds generally used as bleach accelerators, which are hereinafter referred to as the bleach accelerators of this invention.
Typical examples of the bleach accelerators of this invention may include, for example, the following, but by no means limited to these.
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. I-2, 1-4 to -7, 1-9 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, II-81 to -84, II-86 to -99, II-101, 11-102, II-104 to -110, II-112 to -119, II-121 to -124, II-126, II-128 to -144, 11-146, II-148 to -155, II-157, III-4, III-6 to -8, III-10, III-11, 111-13, 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.
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.
The present compounds having the above general formulae (I) to (IX) when added to a bleaching solution may be added and dissolved as such, but generally added after previously dissolved in water, an alkali, an organic acid, etc. and, where necessary, they may be added as dissolved in an organic solvent such as methanol,. ethanol or acetone to produce no influence upon their bleaching effect and the above-depicted effects.
A processing time for bleaching of a light-sensitive silver halide color photographic material with the present bleaching solution is preferably short in order to exert the present effects more effectively. Preferable bleaching time is 6 minutes or shorter, more preferably it is 4 minutes or shorter.
The present bleaching solution may be employed at a pH value of 0.2 to 9.5, preferably 2.0 to 8.0, more preferably 4.0 to 7.0. Processing temperature may be 80 °C or lower, desirably 55 °C or lower for preventing evaporation and other.
Generally, the present bleaching solution may contain a halide such as ammonium bromide and the like.
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.
The aromatic primary amine color developing agent which may be preferably employed in the present color developing solution may include various agents widely employed in a variety of color photographic processings. Such developing agents may involve aminophenol- and p-phenylenediamine-type derivatives.
These compounds may be generally employed in the form of a salt, e.g., hydrochloride or sulfate rather stable than the free form. They may be usually employed at a concentration of about 0.1 g to about 50 g per one litre of a color developer, more preferably about 1 g to about 1.5 g per one litre of the developer.
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-l,4-dimethylbenzene and the like.
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.
In this formula, 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. In the case of alkyl groups, there is mentioned preferably an alkyl group substituted with an aryl group. At least one of ^R ₁₄ and R₁₅is 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 ⁅(CH₂)_q-O⁆R₁₆, 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.
Examples of the compounds having the above general formula [X] are given below, but the present compounds are not limited thereto.
[Exemplary Compound]
The p-phenylenediamine derivatives having the above general formula (X) may be employed as salts with an organic or inorganic acid and, for example, one may employ hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, oxalate, benzenedisulfonate and the like.
The color developing solution which may be employed in this invention may optionally further contain various components commonly applied, for example, an alkali agent such as sodium hydroxide, sodium carbonate and the like; an alkali metal sulfite; an alkali metal hydrosulfite; an alkali metal thiocyanate, an alkali metal halide; benzyl alcohol; a softening agent; a thickner; a developing accelerator; and the like.
Next, cyan coupler according to this invention will be described below.
The cyan coupler of this invention can be represented by Formula (C) shown below.
Formula (C)
wherein ^R ₂₁ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
Herein, R₂₁ 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.).
Into R₂₁ 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.
^R ₂₁ 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.
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 SO₂ R₂₅, a halogen atom (such as fluorine, chlorine, bromine, etc.), -CF₃, -NO₂, -C^N, -COR25, -COOR₂₅, -SO₂₅ ^OR ₂₅₁
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.
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, -SO₂ R₂₇ (R₂₇ is an alkyl group), a halogen atom or trifluoromethyl.
Preferred examples of the ballast group represented by R₂₁ include a group represented by Formula (C - 1)) shown below.
Formula (C - 1)):
In the formula, J represents an oxygen atom or a sulfonyl group; K represents an integer of 0 to 4; 1 represents ⁰ or ¹; and ^R ₂₉ 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 2J carbon atoms or a phenylaminosulfonyl group, etc.
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.
Specific exemplary compounds for the cyan coupler represented by Formula (C) of this invention are shown below, but by no means limited to these.
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.
The cyan couplers represented by Formula(s) (I) and/or (II) 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.
The photographic material, which is particularly preferred 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 following formula (M).
Formula (M):
wherein Z represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring which may be unsubstituted or substituted; X represents a group eliminatable through the reaction with an oxidized product of a color developing agent; and R represents a hydrogen atom or a substituent.
While R in formula(M) represents a hydrogen atom or a substituent. As the substitutent represented by R in formula (M), there may be mentioned, for example, 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 heterocyclyloxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamino group, an acylamino group, a sulfonamide group, an imide group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group and a heterocyclicthio group.
As halogen atoms, for example, chlorine atom, bromine atom may be used, particularly preferably chlorine atom.
The alkyl group represented by R may include preferably those having 1 to 32 carbon atoms, the alkenyl group or the alkynyl group those having 2 to 32 carbon atoms and the cycloalkyl group or the cycloalkenyl group those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkyl group, alkenyl group or alkynyl group may be either straight or branched.
These alkyl group, alkenyl group, alkynyl group, cycloalkyl group and cycloalkenyl group may also have substituents [e.g. an aryl group, a cyano group, a halogen atom, a heterocyclic ring, a cycloalkyl group, a cycloalkenyl group, a spiro ring compound residual group, a bridged hydrocarbon compound residual group; otherwise those substituted through a carbonyl group such as an acyl group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group and an aryloxycarbonyl group; further those substituted through a hetero atom, specifically those substituted through an oxygen atom such as of a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, etc.; those substituted through a nitrogen atom such as of a nitro group, an amino (including a dialkylamino group, etc.), a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an acylamino group, a sulfonamide group, an imide group, a ureido group, etc.; those substituted through a sulfur atom such as of an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, etc.; and those substituted through a phosphorus atom such as of a phosphonyl group, etc.].
More specifically, there may be included, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a pentadecyl group, a heptadecyl group, a 1-hexynonyl group, a l,l'-dipentylnonyl group, a 2-chloro-t-butyl group, a trifluoromethyl group, a 1-ethoxytridecyl group, a 1-methoxyisopropyl group, a methanesulfonylethyl group, a 2,4-di-t-amylphenoxymethyl group, an anilino group, a 1-phenylisopropyl group, a 3-m-butanesulfoneaminophenoxypropyl group, a 3,4'-{a-[4"-(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino} phenylpropyl group, a 3-{4'-[a-(2",4"-di-t-amylphenoxy)-butaneamidolphenyl}propyl group, a 4-[a-(o-chloro- phenoxy)tetradecaneamidophenoxy]propyl group, an allyl group, a cyclopentyl group, a cyclohexyl group, and so on.
The aryl group represented by R may preferably be a phenyl group, which may also have a substituent (e.g. an alkyl group, an alkoxy group, an acylamino group, etc.).
More specifically, there may be included a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, a 4-tetradecaneamidophenyl group, a hexadecyloxyphenyl group, a 4'-[a-(4"-t-butylphenoxy)tetra- decaneamidoJphenyl group and the like.
The heterocyclic group represented by R may preferably be a 5- to 7-membered ring, which may either be substituted or fused. More specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, etc. may be mentioned.
The acyl group represented by R may be, for example, an alkylcarbonyl group such as an acetyl group, a phenylacetyl group, a dodecanoyl group, an a-2,4-di-t-amylphenoxybutanoyl group and the like; an arylcarbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, a p-chlorobenzoyl group and the like.
The sulfonyl group represented by R may include alkylsulfonyl groups such as a methylsulfonyl group, a dodecylsulfonyl group and the like; arylsulfonyl groups such as a benzenesulfonyl group, a p-toluenesulfonyl group and the like.
Examples of. the sulfinyl group represented by R are alkylsulfinyl groups such as an ethylsulfinyl group, an octylsulfinyl group, a 3-phenoxybutylsulfinyl group and the like; arylsulfinyl groups such as a phenyl- sulfinyl group, a m-pentadecylphenylsulfinyl group and the like.
The phosphonyl group represented by R may be exemplified by alkylphosphonyl groups such as a butyl- octylphosphonyl group and the like; alkoxyphosphonyl groups such as an octyloxyphosphonyl group and the like; and aryloxyphosphonyl groups such as a phenoxyphosphonyl group and the like; and arylphosphonyl groups such as a phenylphosphonyl group and the like.
The carbamoyl group represented by R may be substituted by an alkyl group, an aryl group (preferably a phenyl group), etc., including, for example, an N-methylcarbamoyl group, an N,N-dibutylcarbamoyl group, an N-(2-pentadecyloctylethyl)carbamoyl group, an N-ethyl-N-dodecylcarbamoyl group, an N-{3-(2,4-di-t-amylphenoxy)-propyl}carbamoyl group and the like.
The sulfamoyl group represented by R may be substituted by an alkyl group, an aryl group (preferably a phenyl group), etc., including, for example, an N-propylsulfamoyl group, an N,N-diethylsulfamoyl group, an N-(2-pentadecyloxyethyl)sulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group, an N-phenylsulfamoyl group and the like.
The spiro compound residual group represented by R may be, for example, spiro[3.3]heptan-l-yl and the like.
The bridged hydrocarbon residual group represented by _R may be, for example, bicyclo[2.2.llheptan-1-yl, tricyclo-[3.3.1.1³1⁷]decan-1-yl, 7,7-dimethylbicyclo-[2.2.1]heptan-1-yl and the like.
The alkoxy group represented by R may be substituted by those as mentioned above as substituents for alkyl groups, including a methoxy group, a propoxy group, a 2-ethoxyethoxy group, a pentadecyloxy group, a 2-dodecyloxyethoxy group, a phenethyloxyethoxy group and the like.
The aryloxy group represented by.R may preferably be a phenyloxy group of which the aryl nucleus may be further substituted by those as mentioned above as substituents or atoms for the aryl groups, including, for example, a phenoxy group, a p-t-butylphenoxy group, a m-pentadecylphenoxy group and the like.
The heterocyclyloxy group represented by R may preferably be one having a 5- to 7-membered hetero ring, which hetero ring may further have substituents, including a 3,4,5,6-tetrahydropyranyl-2-oxy group, a l-phenyltetrazole-5-oxy group and the like.
The siloxy group represented by R may further be substituted by an alkyl group, etc., including a siloxy group, a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group and.the like.
The acyloxy group represented by R may be exemplified by an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., which may further have substituents, including specifically an acetyloxy group, an a-c_hloroacetyloxy group, a benzoyloxy group and the like.
The carbamoyloxy group represented by R may be substituted by an alkyl group, an aryl group, etc., including an N-ethylcarbamoyloxy group, an N,N-diethyl- carbamoyloxy group, an N-phenylcarbamoyloxy group and the like.
The amino group represented by R may be substituted by an alkyl group, an aryl group (preferably a phenyl group), etc., including an ethylamino group, an anilino group, a m-chloroanilino group, a 3-penta- decyloxycarbonylanilino group, a 2-chloro-5-hexadecane- amidoanilino group and the like.
The acylamino group represented by R may include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), etc., which may further have substituents, specifically an acetamide group, an a-ethylpropaneamide group, an N-phenylacetamide group, a dodecaneamide group, a 2,4-di-t-amylphenoxy- acetoamide group, an a-3-t-butyl-4-hydroxyphenoxybutane- amide group and the like.
The sulfonamide group represented by R may include an alkylsulfonylamino group, an arylsulfonylamino group, etc., which may further have substituents, specifically a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, a 2-methoxy-5-t-amylbenzenesulfonamide and the like.
The imide group represented by R may be either open-chained or cyclic, which may also have substituents, as exemplified by a succinimide group, a 3-heptadecyl- succinimide group, a.phthalimide group, a glutarimide group and the like.
The ureido group represented by R may be substituted by an alkyl group, an aryl group (preferably a phenyl group), etc., including an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group, an N-p-tolylureido group and the like.
The sulfamoylamino group represented by R may be substituted by an alkyl group, an aryl group (preferably a phenyl group), etc., including an N,N-dibutylsulfamoyl- amino group, an N-methylsulfamoylamino group, an N-phenylsulfamoylamino group and the like.
The alkoxycarbonylamino group represented by R may further have substituents, including a methoxycarbonyl- amino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group and the like.
The aryloxycarbonylamino group represented by R may have substituents, and may include a phenoxycarbonyl- amino group, a 4-methylphenoxycarbonylamino group and the like.
The alkoxycarbonyl group represented by R may further have substituents, and may include a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxy- methoxycarbonyloxy group, an benzyloxycarbonyl group and the like.
The aryloxycarbonyl group represented by R may further have substituents, and may include a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, a m-pentadecyloxyphenoxycarbonyl group and the like.
The alkylthio group represented by R may further have substituents, and may include an eLhyltnio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, a 3-phenoxypropylthio group and the like.
The arylthio group represented by R may preferably be a phenylthio group, which may further have substituents, and may include, for example, a phenylthio group, a p-methoxyphenylthio group, a 2-t-octylphenylthio group, a 3-octadecylphenylthio group, a 2-carboxyphenylthio group, a p-acetaminophenylthio group and the like.
The heterocyclicthio group represented by R may preferably be a 5- to 7-membered heterocyclicthio group, which may further have a fused ring or have substituents, including, for example, a 2-pyridylthio group, a 2-benzo- thiazolylthio group, a 2,4-di-phenoxy-l,3,5-triazole-6-thio group and the like.
The substituents eliminatable through the reaction with the oxidized product of a color developing agent represented by X may include halogen atoms (e.g. a chlorine atom, a bromine atom, a fluorine atom, etc.) and also groups substituted through a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom.
The group substituted through a carbon atom may include the groups represented by the formula:
wherein R₁' has the same meaning as the above R, Z' has the same meaning as the above Z, R₂' and ^R ₃' each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group, a hydroxymethyl group and a triphenylmethyl group.
The group substituted through an oxygen atom may include an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, an alkoxyoxalyloxy group.
Said alkoxy group may further have substituents, including an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group, a p-chloro- benzyloxy group and the like.
Said aryloxy group may preferably be a phenoxy group, which aryl group may further have substituents. Specific examples may include a phenoxy group, a 3-methylphenoxy group, a 3-dodecylphenoxy group, a 4- methanesulfonamidophenoxy group, a 4-[a-(3'-pentadecylphenoxy)butaneamido]-phenoxy group, a hexadecylcarbamoyl- methoxy group, a 4-cyanophenoxy group, a 4-methane- sulfonylphenoxy group, a 1-naphthyloxy group, a p-methoxyphenoxy group and the like.
Said heterocyclyloxy group may preferably be a 5-to 7-membered heterocyclicoxy group, which may be a fused ring or have substituents. Specifically, a I-phenyl- tetrazol- yloxy group, a 2-benzothiazolyloxy group and the like may be included.
Said acyloxy group may be exemplified by an alkylcarbonyloxy group such as an acetoxy group, a butanoyloxy group, etc.; an alkenylcarbonyloxy group such as a cinnamoyloxy group; an arylcarbonyloxy group such as a benzoyloxy group.
Said sulfonyloxy group may be, for example, a butanesulfonyloxy group, a methanesulfonyloxy group and the like.
Said alkoxycarbonyloxy group may be, for example, an ethoxycarbonyloxy group, a benzyloxycarbonyloxy group and the like.
Said aryloxycarbonyl group may be, for example, a phenoxycarbonyloxy group and the like.
Said alkyloxalyloxy group may be, for example, a methyloxalyloxy group.
Said alkoxyoxalyloxy group may be, for example, an ethoxyoxalyloxy group and the like.
The group substituted through a sulfur atom may include an alkylthio group, an arylthio group, a heterocyclicthio group, an alkyloxythiocarbonylthio groups.
Said alkylthio group may include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group, a benzylthio group and the like.
Said arylthio group may include a phenylthio group, a 4-methanesulfonamidophenylthio group, a 4-dodecylphenethylthio group, a 4-nonafluoropentaneamido- phenethylthio group, a 4-carboxyphenylthio group, a 2- ethoxy-5-t-butylphenylthio group and the like.
Said heterocyclicthio group may be, for example, a l-phenyl-l,2,3,4-tetrazolyl-5-thio group, a 2-benzothia- zolylthio group and the like.
Said alkyloxythiocarbonylthio group may include a dodecyloxythiocarbonylthio group and the like.
The group substituted through a nitrogen atom may include, for example, those represented by the formula:
Here, R₄' and R_S' each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group or an alkoxycarbonyl group. R₄' and R₅' may be bonded to each other to form a hetero ring. However, _R4' and _R5' cannot both be hydrogen atoms.
Said alkyl group may be either straight or branched, having preferably 1 to 22 carbon atoms. Also, the alkyl group may have substituents such as an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamide group, an imino group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkyloxycarbonylamino group, an aryloxycarbonylamino group, a hydroxyl group, a carboxyl group, a cyano group, halogen atoms, etc. Typical examples of said alkyl group may include an ethyl group, an octyl group, a 2-ethylhexyl group, a 2-chloroethyl group and the like.
The aryl group represented by R₄' or R₅' may preferably have 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group, which aryl group may also have substituents such as those as mentioned above for substituents on the alkyl group represented by R₄' or R₅' and alkyl groups. Typical examples of said aryl group may be, for example, a phenyl group, a 1-naphtyl group, a 4-methylsulfonylphenyl group and the like.
The heterocyclic group represented by R₄' or R₅' may preferably a 5- or 6-membered ring, which may be a fused ring or have substituents. Typical examples may include a 2-furyl group, a 2-quinolyl group, a 2- pyrimidyl group, a 2-benzothiazolyl group, a 2-pyridyl group and the like.
The sulfamoyl group represented by R. or R₅' may include an N-alkylsulfamoyl group, an N,N-dialkylsulfa- moyl group, an N-arylsulfamoyl group, an N,N-diarylsulfa- moyl group and the like, and these alkyl and aryl groups may have substituents as mentioned above for the alkyl groups and aryl groups. Typical examples of the sulfamoyl group are, for example, an N,N-diethylsulfamoyl group, an N-methylsulfamoyl group, an N-dodecylsulfamoyl group, an N-p-tolylsulfamoyl group and the like.
The carbamoyl group represented by R₄' or R₅' may include an N-alkylcarbamoyl group, an N,N-dialkylcarbamoyl group, an N-arylcarbamoyl group, an N,N-diarylcarba- moyl group and the like, and these alkyl and aryl groups may have substituents as mentioned above for the alkyl groups and aryl groups. Typical examples of the carbamoyl group are an N,N-diethylcarbamoyl group, an N-methylcarbamoyl group, an N-dodecylcarbamoyl group, an N-p-cyanophenylcarbamoyl group, an N-p-tolylcarbamoyl group and the like.
The acyl group represented by R₄ ¹ or R₅' may include an alkylcarbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, which alkyl group, aryl group and heterocyclic group may have substituents. Typical examples of the acyl group are a hexafluorobuta- noyl group, a 2,3,4,5,6-pentafluorobenzoyl group, an acetyl group, a benzoyl group, a naphthoyl group, a 2-furylcarbonyl group and the like.
The sulfonyl group represented by R₄' or R₅' may be, for example, an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic sulfonyl group, which may also have substituents, including specifically an ethanesulfonyl group, a benzenesulfonyl group, an octane- sulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group and'the like.
The aryloxycarbonyl group represented by R₄' or R₅' may have substituents as mentioned for the above aryl group, including specifically a phenoxycarbonyl group and the like.
The alkoxycarbonyl group represented by R₄' or R₅' may have substituents as mentioned for the above alkyl group, and its specific examples are a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group and the like.
The heterocyclic ring formed by bonding between R₄' and R₅' may preferably be a 5- or 6-membered ring, which may be either saturated or unsaturated, either has aromaticity or not, or may also be a fused ring. Said heterocyclic ring may include, for example, an N-phthalimide group, an N-succinimide group, a 4-N-urazolyl group, a 1-N-hydantoinyl group, a 3-N-2,4-dioxooxa- zolidinyl group, a 2-N-1,1-dioxo-3-(2H)-oxo-1,2-benzthia- zolyl group, a 1-pyrrolyl group, a 1-pyrrolidinyl group, a 1-pyrazolyl group, a 1-pyrazolidinyl group, a 1-piperidinyl group, a 1-pyrrolinyl group, a 1-imidazolyl group, a 1-imidazolinyl group, a 1-indolyl group, a 1-isoindolinyl group, a 2-isoindolyl group, a 2-iso- indolinyl group, a 1-benzotriazolyl group, a 1-benzo- imidazolyl group, a 1-(1,2,4-triazolyl) group, a 1-(1,2,3_-triazolyl) group, a 1-(1,2,3,4-tetrazolyl) group, an N-morpholinyl group, a 1,2,3,4-tetrahydroquinolyl group, a 2-oxo-l-pyrrolidinyl group, a 2-lH-pyrridone group, a phthaladione group, a 2-oxo-l-piperidinyl group, etc. These heterocyclic groups may be substituted by an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an acyl group, a sulfonyl group, an alkylamino group, an arylamino group, an acylamino group, a sulfon- amino group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an arylthio group, a ureido group, an alkoxycarbonyl group, an aryloxycarbonyl group, an imide group, a nitro group, a cyano group, a carboxyl group or halogen atoms.
The nitrogen-containing heterocyclic ring formed by Z and Z' may include a pyrazole ring, a imidazole ring, a triazole ring or a tetrazole ring, etc. and the substituents which may be possessed by the above rings may include those as mentioned for the above R.
When the substituent (e.g. R, R₁ to R₈) 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 Z_l 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).
The compounds represented by the formula (M) can be also represented specifically by the following formulae (M - I) through (M - VI).
In the above formulae (M - I) to (M - VI)), R₁ to _R8 and X have the same meanings as the above R and X.
Of the compounds represented by the formula (M), those represented by the following formula (M - VII) are preferred.
wherein R₁, X and Z₁ have the same meanings as R, X and Z in the formula (M.
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.
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.

Of the subntituents R and R₁ on the above heterocyclic ring, most preferred are those represented by the formula (M - VIII) shown below:
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.
Also, at least two of said R₉, R₁₀ and R₁₁, for- example, Rg 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.
The groups represented by Rg 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.
Also, examples of the ring formed by bonding between R₉ and R₁₀, 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.
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 Rg and R₁₀ are bonded together with the root carbon atom to form a cycloalkyl group.

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.
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.
The magenta coupler represented by formula (M) may include the specific compound enumerated below.
Magenta couplers for photography which may be combined with the magenta coupler of this invention may include compounds of pyrazolone type, pyrazolinobenz- imidazole 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.
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.
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.
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).
The aromatic sulfonyl group represented by Formula (A) will be described below in detail Formula (A):
In the formula, ^R _l represents an aliphatic group, an aryl group or a heterocyclic group; m represents an integer of 1 or 2; and R₁ 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).
In Formula (A), to describe ^R _l 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.
Of the aromatic sulfonyl group represented by Formula (A), preferable is the compound represented by the following formula:
In the formula, R₁₂ and R₁₃ each represent a group having the same meaning as defined for R₁ and R₂ in Formula (A).
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.
Typical examples of the magenta coupler used in this invention are shown below, but by no means limited to these.
The pyrazoloazole type magenta coupler having at least one aromatic sulfonyl group represented by Formula (A) in the molecular structure of this invention can be synthesized by making reference to Journal of the Chemical Society, Perkin I (1977), 2047-2052, U.S. Patent No. 3,725,067, Japanese Unexamined Patent Publications No. 99437/1984, No. 42045/1983, No. 162548/1984, No. 171956/1984, No. 33552/1985, No. 43659/1985, No. 172982/1985 and No. 190779/1985, etc.
The pyrazoloazole type magenta coupler of this invention can be used generally in the range of 1 x 10^-3 mole to 1.5 moles, preferably 1 x 10-2 mole to 1 mole, per mole of silver halide.
The pyrazoloazole type magenta coupler of this invention can be used in combination with other type of magenta couplers.
The pyrazoloazole type magenta coupler of this invention may be added to a desired hydrophilic colloid layer after dissolving it in an organic solvent having a high boiling point of about 150°C or more optionally together with a low boiling solvent and/or a water soluble organic solvent and effecting emulsification dispersion of the solution in a hydrophilic binder such as an aqueous gelatin solution with use of a surface active agent. There may be inserted a step of removing the dispersing solution, or at the same time of the dispersion, the low boiling organic solvent.
Preferred embodiment of this invention is characterized by processing the light-sensitive silver halide color photographic material containing the above coupler according to this invention in the above bleaching solution according to this invention. In the processing by the bleaching solution of this invention, however, the bleaching solution may be used as a - processing solution to effect bleaching immediately after color development of the light-sensitive silver halide color photographic material containing the above coupler of this invention, or may be used as a bleaching solution after color developing and processing such as washing, rinsing or stopping have been carried out.
Also, after processing by use of the bleaching solution of this invention, fixing, washing and thereafter stabilizing may be carried out. This invention can be also applied to a multiple stage counter current stabilizing technique wherein the washing step is omitted or the amount of water is extremely reduced as disclosed in Japanese Unexamined Patent Publication No. 8543/1982, or a technique wherein the processing is carried out by use of a washing-substitutive processing solution as disclosed in Japanese Unexamined Patent Publication No. 14834/1983. In addition to the steps of color developing, bleaching, fixing, washing and so forth, there may be added every sort of auxiliary steps such as hardening, neutralizing, black and white developing, reversing and a step of washing with a small amount of water, as occasion demands.
As yellow couplers for photography, conventionally used are open-chain ketomethylene compounds, and there can be used benzoylacetanilide type yellow couplers and pivaroylacetanilide type couplers widely used in general. Two equivalent type yellow couplers wherein a carbon atom at the coupling position is substituted with a substituent eliminatable through the coupling reaction can be also used. Examples of these, together with synthesis methods thereof, are disclosed in U.S. Patents No. 2,875,057, No. 3,265,506, No. 3,664,841, No. 3,408,194, No. 3,277,155, No. 3,447,928 and No. 3,415,652, Japanese Patent Publication No. 13576/1974, Japanese Unexamined Patent Publications No. 29432/1973, No. 68834/1973, No. 10736/1974, No. 122335/1974, No. 28834/1975 and No. 132926/1975, etc.
The above nondiffusion couplers in this invention may be used generally in an amount of 0.05 mole to 2.0 moles per mole of silver in the light-sensitive silver halide emulsion layer.
In this invention, besides the above nondiffusion couplers, a DIR compound may be preferably used.
Besides the DIR compound, a compound capable of releasing a development restrainer along with development may be also included in this invention, which may include, for example, the compounds disclosed in U.S. Patents No. 3,297,445 and No. 3,379,529, West German Patent Publication (OLS) No. 24 17 914, Japanese Unexamined Patent Publications No. 15271/1977, No. 9116/1978, No. 123838/1984 and No. 127038/1984, etc.
The DIR compound used in this invention is a compound capable of releasing a development restrainer through the reaction with an oxidized product of a color developing agent.
Such a DIR compound may typically include DIR couplers wherein a group capable of forming a compound having a development restraining action has been introduced to a coupler active site when eliminated from the active site, which are disclosed, for example, in British Patent No. 935,454, U.S. Patents No. 3,227,554, No. 4,095,984 and No. 4,149,886, etc.
The above DIR couplers have a property that a coupler mother nucleus may form a dye and, on the other hand, a developing restrainer is released when coupled with an oxidized product of a color developing agent. In this invention, also included is such a compound capable of releasing a development restrainer but not forming any dye when coupled with an oxidized product of a color developing agent, as disclosed in U.S. Patents No. 3,652,345, No. 3,928,041, No. 3,958,993, No. 3,961,959 and No. 4,052,213, Japanese Unexamined Patent Publications No. 110529/1978, No. 13333/1979 and No. 161237/1980, etc.
Still also included in this invention is the so-called timing DIR compound which is a compound such that a mother nucleus may form a dye or colorless compound when reacted with an oxidized product of a color developing agent, and on the other hand, an eliminated timing group may release a development restrainer through the intramolecular nucleophilic substitutive reaction or elimination reaction. As disclosed in Japanese Unexamined Patent Publication Nos. 145135/1979, 114946/1979 and 154234/1982.
There may be also included a timing DIR compound wherein the timing group as mentioned above has been attached onto a coupler mother nucleus capable of forming a perfectly diffusing dye when reacted with an oxidized product of a color developing agent, as disclosed in Japanese Unexamined Patent Publications No 160954/1983 and No. 162949/1983.
The DIR compound contained in the light-sensitive material may be used preferably in an amount ranging between 1 x 10^-4 mole to 10 x 10 ¹ mole per mole of silver.
The color developing solution used in this invention may further contain a variety of components usually added, for example, every sort of additives such as alkali agents, every sort of salts, antifoggants,' development accelerators, organic solvents for increasing solubility of a developing agent, chelating agents, brightening agents, auxiliary developing agents, competing couplers, fogging agents, colored couplers, DIR couplers, anti-stain agents, anti-sludge agents and interlayer effect-accelerating agents.
The fixing solution may contain additives usually used in a fixing solution, including silver halide-fixing agents, pH-buffering agents, brightening agents, anti-foaming agents, surface active agents, preservatives, chelating agents, organic solvents, etc.
In the emulsion layers of the light-sensitive color photographic material, couplers conventionally used can be appropriately used besides the above coupler of this invention.
There can be also used compounds capable of releasing a photographically meaningful fragment such as colored couplers having a color correction effect, agents for accelerating development by the coupling reaction of a competing coupler with an oxidized product of a developing agent, bleach accelerators, developing agents, silver halide solvents, toning agents, hardening agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers.
The light-sensitive material may be provided with auxiliary layers such as a filter layer, an anti-halation layer and an anti-irradiation layer. These layers and/or the emulsion layers may also contain a dye that can be flowed out of a light-sensitive material or bleached during developing processing.
To the light-sensitive material, a matte agent, a lubricant, an image stabilizing agent, a surface active agent, a color fog preventive agent, a development accelerator, a development restrainer and a bleach accelerator can be added.
The light-sensitive material which may be employed in this invention is a base having coated thereon a silver halide emulsion layer and a non-light-sensitive layer (i.e., a non-emulsion layer). As the silver halide emulsion layer, there may be any of the layers using any sulver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide. The emulsion layer and non-light-sensitive layer may further contain any couplers, additives and others well-known in - a photographic field; there may be optionally incorporated, for example, a yellow dye-forming coupler, a magenta dye-forming coupler, a cyan dye-forming coupler, a stabilizer, a sensitizing dye, a gold compound high-boiling organic solvent, an antifoggant, a color image antidiscoloring agent, an anti-color staining agent, a brightening agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a lubricant, an ultra violet absorber and the like.
The light-sensitive material which may be employed in the present method may be prepared by coating onto a base treated with corona charge, flame or irradiation of ultra violet ray or via a subbing layer or an intermediate layer construction layers of a emulsion layer containing various additives mentioned above as required, a non-light-sensitive layer and other layers. As the base or support which may be advantageously employed, there may be mentioned, for example, Baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent base, e.g., glass plate, provided with a reflective layer or using a reflective layer, cellulose acetate, cellulose nitrate or a polyester film, e.g., polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film and the like.
Most of the said silver halide emulsion layer and non-light-sensitive layers may be usually composed of a hydrophilic colloid layer containing a hydrophilic binder. As the hydrophilic binder, there may be .preferably used gelatin or gelatin derivatives such as acylated gelatin, quanidyl gelatin, phenylcarbamyl gelatin, phthalated gelatin, cyanoethanolated gelatin, esterified gelatin and the like.
As the hardening agent for hardening the hydrophilic colloid layer, there may be employed alone or in combination, for example, chromic acid salts (chromium alum, chromium acetate etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde etc.), N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, l,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogenic acids (mucochloric acid, mucophenoxychloric acid etc.) and the like.
Also, this invention is particularly effective in the light-sensitive material having dispersed therein a coupler contained in a high-boiling organic solvent, i.e. the so-called "oil protect type" material. As the high-boiling organic solvent, there may be employed for greater effect of this invention, for example, organic acid amides, carbamates, esters, ketones, urea derivatives and the like; particularly, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, di-propylphthalate, di-butylphthalate, di-n-octyl phthalate, diisooctyl phthalate, diamyl phthalate, dinonyl phthalate, diisodecyl phthalate and the like; phosphoric acid esters such as tricresyl phosphate', triphenyl phosphate, tri-(2-ethylhexyl)phosphate, trinonyl phosphate and the like; sebacic acid esters such as dioctyl sebacate, di-(2-ethylhexyl)sebacate, diisodecyl sebacate and the like; glycerol esters such as glycerol tripropionate, glycerol tributylate and the like; as well as adipic acid esters, glutaric acid esters, succinic acid esters, maleic acid esters, fumaric acid esters, citric acid esters, phenol derivatives, e.g., di-tert-amylphenol, n-octylphenol etc.
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).
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.
The definitions of the general formula [XI] are illustrated in detail.
In the formula, Z₁₁ and Z₂₁ 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.
Preferable embodiment is that Z₁₁ and Z₂₁ 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 preterably, 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 saving 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.
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.
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.
The sensitizing dye having the above general formula (XI) may be added to an emulsion at any point having 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.
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.
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.

Example 1

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.
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.
The color developing solution, bleaching solution, fixing solution and stabilizing solution as prescribed below were employed.
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]
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 replenisherl
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]
Water was added to make up a 1 litre volume.
[Color development replenisher]
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.
The bleaching replenisher, fixing replenisher and stabilizing replenisher were used with the same compositions as in the respective tank solutions. Also, concentrations of the ethylenediaminetetraacetic acid as one example of the organic acid involved in the bleaching solution varied as indicated in the following Table 1.
The color development replenisher was supplied to the color developing solution at 1.5 ℓ per 1 m² of the negative color film and the fixing replenisher to the fixing bath at 1 per 1 m² of the negative color film. Also, the stabilizing replenisher was supplied at 1 ℓ per 1 _m ² of the negative color film and washing water was flown at 15 1 per 1 m² of the film. The bleaching replenisher was supplied at a replenished volume as indicated in the following Table 1.
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.
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 ml 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

Continuous processing was carried out by using the same negative color film as in Example 1 according to the same processing steps as in Example 1, except that a composition of the bleaching replenisher was changed as prescribed below to correct dilution of the bleaching solution due to the color developer taken into the bleaching solution.

[Bleaching replenisher - 1]

(Ethylenediaminetetraacetato)iron (III)
Water was added to make up a 1 litre volume and a . pH value was adjusted to 5.7 with acetic acid and aqueous ammonia.

[Bleaching replenisher - 2]

(Ethvlenediaminetetraacetato)iron (III)
Water was added to make up a 1 litre volume and a pH value was adjusted to 5.7 with acetic acid and aqueous ammonia.

[Bleaching replenisher - 3]

[Bleaching replenisher - 4]

(Ethylenediaminetetraacetato)iron (III)
Water was added to make up a 1 litre volume and a pH value was adjusted to 5.7 with acetic acid and aqueous ammonia.

[Bleaching replenisher - 5]

(Ethvlenediaminetetraacetato)iron (III)
Water was added to make up a 1 litre volume and a pH value was adjusted to 5.7 with acetic acid and aqueous ammonia.
In this instance, all concentrations of the ethylenediaminetetraacetic acid were made to be 5 mole % of the (ethylenediaminetetraacetato)iron (III) complex and a pH value was properly adjusted to pH 6.0 with acetic acid and aqueous ammonia. The results are shown in Table 2.
As shown in the above Table 2, even where each component in the bleaching solution was corrected for the color developer taken into the bleaching solution with the negative color film or where a replenished amount was lowered as in Example 1, there were obtained the favourable results wherein recoloring and desilvering properties of cyan dye are not inferior.

Example 3

Following the same procedures as in Example 1, tests were conducted except that each of the Exemplary Compounds (II - 28), (II - 144), (III - 34), (III - 2), (III - 38), (V - 71), (V - 75) and (VIII - 1) was added at a rate of 2 g/ℓ to the bleaching solutions in Example 1, Experiment Nos. 16 to 20 and the bleaching processing time was 2 min. 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 4

By replacing the cyan coupler (C' - 1) employed for the film sample as prepared in Example 1 by the Exemplary cyan couplers of this invention (C - 1), (C - 2), (C - 3), (C - 8), (C - 23) and (C - 39), there were prepared test film samples. The film samples were tested according to the same procedures as in Example 1 except that the bleaching solutions of Example 1, test Nos. 16 to 20 were employed and the bleaching processing time was 2 minutes and 30 seconds. As a result, though the bleaching processing time was shortened, recoloring property of cyan dye could be in every case improved by about 40 to 60 %, while a residual silver amount could be reduced by about 20 %.

Example 5

Film samples were prepared by applying the Exemplary Compound (XI - 1) or (X - 4) to the green-sensitive silver halide emulsion layer of the film sample as prepared in Example 1 and then tested in the same manner as in Example 1. Where the bleaching solution of this invention was employed, a residual silver amount was reduced by about 5 to 10 %.

Example 6

An antihalation layer and a gelatin layer were coated over a triacetate film base and there were then coated thereover, in turn, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, a blue-sensitive silver halide emulsion layer and a protective layer so that a total silver amount may beocme 72 mg per 100 cm^2. Said emulsion layers contained individually a mole % of silver iodide of about 4.3 % of silver iodobromide, while the yellow coupler (Y - 1) as used in 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'-l) as used in Example 1 for the red-sensitive silver halide emulsion layer.
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 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.
In the steps, continuous running processing was done for 40 m²of 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.
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 7

Comparative samples were prepared by replacing the magenta coupler (M - 5) employed for the film sample of Example 6 with the comparative magenta coupler (M' - 1) as used in Example 6 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 6, test No. 49. 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. Magenta coupler (M^{I -} 2)

Example 8

Following the same procedures as in Example 6, 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 6, test Nos. 46 to 50, 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 9

Following the same procedures as in Example 6, 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 6 were effected. As a result, a residual silver amount was reduced by 5 to 10 % when the present bleaching solution was applied.

Example 10

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.
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.
The color developing solution, bleaching solution, fixing solution and stabilizing solution as prescribed below were employed.
pH value was adjusted to 10.00 with potassium hydroxide or 20 % sulfuric acid.
[Bleaching solution and bleaching replenisher]

pH value was adjusted to 5.9 with acetic acid with aqueous ammonia.
[Fixing solution and fixing replenisher]
pH value was adjusted to 7.0 with acetic acid and aqueous ammonia.
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.
The bleaching replenisher, fixing replenisher and stabilizing replenisher were used with the same compositions as in the respective tank solutions. Also, concentrations of the ethylenediaminetetraacetic acid as one example of the organic acid involved in the bleaching solution varied as indicated in the following Table 4.
The color development replenisher was supplied to the color developing solution at 1.5 ℓ per 1 m² of the negative color film and the fixing replenisher to the fixing bath at 1 ℓ per 1 m² of the negative color film. Also, the stabilizing replenisher was supplied at 1 ℓ per 1 m² of the negative color film and washing water was flown at 15 1 per 1 m² of the film. The bleaching replenisher was supplied at a replenished volume as indicated in the following Table 4.
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.
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 ml 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 11

Comparative samples were prepared by replacing the magenta coupler (M - 203) employed for the film sample of Example 10 with the comparative magenta coupler (_M' - 1) as used in Example 1 and the comparative magenta coupler (_M' - 2) as used in Example 7. 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 10, test No. 74. Cyan dye density and residual silver amount were measured. Also, magenta stain in unexposed portion was measured.
Results are also shown in Table 5.
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.
There are also found that both the recoloring properties of cyan dye and the residual silver amount were good.

Example 12

Following the same procedures as in Example 10, 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 10, test No. 74 in the amount described in Table 6, respectively, and the bleaching processing time was 3 minutes.
As a result, though the bleaching processing time was shortened, a residual silver amount in every case was reduced.

Example 13

Following the same procedures as in Example 10, 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 10, and then the same tests as in Example 6 were effected. Results are shown in Table 7.
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 14

The same tests as in Example 10, test Mo. 74 were repeated provided for replacing the color developing agent in the color developing solution used in Example 10, test No. 74 (Examplary No. X-2) with the hydrochlorides (D-l) and (D-2) shown below. Further, similar tests were carried out by replacing the color developing agent (X-2) with a sulfate of (X-l), p-toluenesulfonate of (X-4) and p-toluenesulfonate of (X-11).
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.
In Table 8, o represents no generation of tar, represents a little generation of tar and x represents generation of tar to such a degree that a tar adhered to a film.
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 15

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-diaminopropanetetra- acetate). 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.
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

1. In 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, the improvement 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 in a range of not more than 10 mole % of the content of said organic acid ferric complex contained in said bleaching solution; and a replenished amount in said bleaching step is 30 ml to 300 m£ per lm² 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);

General formula (I):

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 R₁ 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,

General Formula (II):

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_l-valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring); X represents =_S, =_O 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 nl to n6 and ml 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 ^R ₂ and R₃, R and R', and R₄ and R₅ each may be combined to form a ring,

General Formula (III):

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,

General Formula (IV):

wherein R₈ and _Rg each represent

; and R_lO 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); G⁹ represents an anion; and n8 represents an integer of 1 to 6,

General Formula (V):

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 Q₁,

General Formula (VI):

wherein 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 ql, 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,

General Formula (VII):

wherein X₂ represents -COOM', -OH, -S0₃M', -CONH₂, -SO₂NH₂, -NH₂, -SH, -CN, -CO₂R₁₆, -SO₂R₁₆, -^OR1₆, -^NR16^Rl7, -SR₁₆, -SO₃R₁₆, -NHCOR₁₆, -NHS0₂R_l6, -OCOR₁₆ or -SO₂R₁₆; Y₂ represents

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,

General Formula (VIII):

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; ^B ₂ 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,

General Formula (IX):

wherein ^R ₂₉ and R₃₀ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R₃₁ 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, wherein at least one layer of said light-sensitive silver halide color photographic material contains a cyan coupler having the general formula (C):

wherein R₂₁ 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, 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 substitutent; X represents a hydrogen atom or a substituent eliminatable through a reaction with an oxidized product of a color developing agent; and R represents a hydrogen atom or a substituent.

5. The method for processing a light-sensitive silver halide color photographic material as claimed in claim 1, wherein at least one layer of said silver halide emulsion layer contains at least one pyrazoloazole series magenta coupler having at least one aromatic sulfonyl group represented by the following formula in the molecular structure:

wherein R₁ 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.

6. The method for processing a light-sensitive silver halide color photographic material as claimed in claim 1, 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 substitutent; X represents a hydrogen atom or a substituent eluminatable through a reaction with an oxidized product of a color developing agent; and R represents a hydrogen atom or a substituent.

7. The method for processing a light-sensitive silver halide color photographic material as claimed in claim 1, 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, -R₈₃OR₈₃OR₈₃- or -R₈₃ZR₈₃-, Z represents

or

R₇₉ to R₈₃ individually represent a substituted or unsubstituted alkylene group, _A2 to _A6 individually represent a hydrogen atom, -OH, -COOM or -PO₃M₂ and M is a hydrogen atom or an alkali metal atom.

8. The method for processing a light-sensitive silver halide color photographic material as claimed in claim 7, 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) l,3-Diaminopropan-2-ol-tetraacetic acid

(XII - 19) Ethylenediaminetetramethylene phosphonic acid

(XIII - 1) Nitrilotriacetic acid

(XIII - 3) Hydroxyethyliminodiacetic acid

(XIII - 5) Nitrilotrimethylene phosphonic acid

9. The method for processing a light-sensitive silver halide color photographic material as claimed in claim 1, 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.

10. The method for processing a light-sensitive silver halide color photographic material as claimed in claim 9, 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.

11. 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).

12. The method for processing a light-sensitive silver halide color photographic material as claimed in claim 1, 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 ⁅(CH₂)-_qO-⁆R₁₆, 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.

13. The method for processing a light-sensitive silver halide color photographic material as claimed in claim 1, 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.