DE3789249T2 - Process for the treatment of a light-sensitive color photographic halide material. - Google Patents

Description

Background of the invention

The present invention relates to a process for producing a silver halide color photographic light-sensitive material. More particularly, it relates to a process for producing a silver halide color photographic light-sensitive material without any deterioration in recoloring property even when a replenished amount of a bleaching agent is reduced.

From FR-A-2276613, JP-A-6-117541, EP-A-0143570 and EP-A-0158369, photographic working processes are known that use bleaching solutions that contain an organic iron(III) complex and an organic acid. From EP-A-0158369, it is also known to refill the bleaching solutions.

Working with light-sensitive materials includes as a basis the two stages of color development and desilvering, and the desilvering stage consists of the bleaching and fixing stage or a bleach-fixing stage. In addition to these stages, rinsing treatments, stabilization treatments and so on can be inserted as additional work stages.

In color development, an exposed silver halide is reduced to silver and, at the same time, an oxidized aromatic primary amine as a color developing agent is subjected to a reaction with a coupler to form a dye. In this process, the halogen ion produced by the development of a silver halide is dissolved in a developing solution and collected therein. Also, the components such as a retarder and the like contained in a silver halide photographic light-sensitive material are dissolved in a color developing solution and collected therein. collected. In the desilvering step, the silver as produced by development is bleached by means of an oxidizing agent, and then all silver salts are removed from the light-sensitive silver halide photographic material as soluble silver salts by a fixing agent.

In a processing solution having bleaching ability for treating a silver halide color photographic light-sensitive material, inorganic oxidizing agents such as red prussinate, dichromic acid salts and the like have been widely used as an oxidizing agent for bleaching an image silver.

With respect to the treatment solution having a bleaching ability and containing such inorganic oxidizing agents, there are several serious disadvantages. For example, prussiate and dichromic acid salts are relatively stronger in terms of their bleaching power of image silver, but tend to decompose under the influence of light and develop a cyan ion and a hexavalent chromium ion which are harmful to humans and exhibit an undesirable property in preventing environmental pollution. In addition, the treatment solution containing such inorganic oxidizing agents has the disadvantage of being difficult to regenerate and reuse the waste water after treatment without discarding it.

In contrast, a processing solution containing an organic acid metal complex such as an aminopolycarboxylic acid metal complex and the like as an oxidizing agent has been used to meet the demands such as less pollution problems, faster treatment, simplification and regeneration of waste water for reuse. However, the processing solution using the organic acid metal complex has a disadvantage of a slow bleaching rate (or oxidation rate) of the image silver (metallic silver) which is oxidized during the development stage due to the slow oxidizing power. For example, an (ethylenediaminetetraacetate)-iron(III) complex, which is believed to exert a strong bleaching power on the aminopolycarboxylic acid metal complexes, has been partially practically used as a bleaching solution or a bleach-fixing bath, but has the disadvantage of insufficient bleaching power and a prolonged bleaching step, in a high-sensitivity silver halide color photographic light-sensitive material containing a silver bromide or silver iodobromide emulsion as a main component, particularly a color paper for photography, a color negative film for photography, a color reversal film for photography and the like, which contain silver iodide having a high silver content as a silver halide.

By treating the photosensitive material as above, a color developing component in the previous bath also tends to adhere to the photosensitive material and thereby be carried into the bleaching bath and accumulate there.

Therefore, in a process for continuously developing a large amount of silver halide photographic light-sensitive materials by means of an automatic developing machine, means for maintaining a given concentration range of components in a processing bath are required in order to avoid deterioration of the performance of a bleaching solution due to the change in component concentrations. As such means, a method of replenishing a replenisher solution has been conventionally employed to dilute unnecessary components and to supplement missing components. By replenishing the replenisher solution, a large volume is necessarily generated to be discarded, and this method therefore leads to great economic problems or environmental pollution. Accordingly, a method has recently been developed in which such replenishers are condensed and converted into a small volume to reduce the overflowing solution, a so-called low-condensation condensed system. Replenishment, or another process wherein a regenerant is added to the overflowing solution for reuse as a replenishment solution.

With particular reference to a bleaching solution or bath, a process has been practically realized in which the iron complex with the organic acid produced by bleaching a developed silver, e.g., the (ethylenediaminetetraacetate)-iron(II) complex, is oxidized under aeration to the (ethylenediaminetetraacetate)-iron(III) complex, i.e., the iron complex of the organic acid, to which a regenerating agent is subsequently added to supplement the missing component and the resulting mixture is used again as a replenisher solution.

Recently, the so-called compact photo lab (also called "mini photo lab") has come onto the market to process in a short time and reduce the cost of collection and delivery, but there is a need to simplify the processing and also to reduce the area for installing a processing machine. There is no interest in a regeneration stage that requires complicated work and control and also additional work space.

Therefore, a compact low-replenishment system is advantageous in which a small replenishment is carried out without a replenishment step; however, an extreme drop in the replenishment amount of the bleaching solution may lead to an increase in the concentration of the color developing components absorbed by the bleaching solution and to the influence of concentration with evaporation being more easily obtained, resulting in a greater accumulation of the color developing components. Thus, when the concentration of the color developing components in a bleaching solution increases, the ratio of contaminating color developing agents such as reducing components, sulfites and the like increases to inhibit the bleaching reaction and, what is more serious, a dye, particularly a cyan dye, may easily enter the corresponding leuco form, thereby causing a disadvantage of insufficient coloring, or easily causing the so-called poor recoloring. This phenomenon may be particularly remarkable in a high-sensitivity photosensitive material having a high silver content and silver iodide as a main component. The regeneration step is essentially a system for reducing a replenishment amount; however, the above-mentioned disadvantage may be difficult to see therein, since aeration can be practiced, whereby substantial aeration is caused due to an extended remaining time in a holding tank and others except the bleaching tank and an extended contact time with air, and a treatment time in the first bleaching step is at least six minutes or longer.

Notwithstanding this, recently, much less refilling has been requested due to lower costs, less pollution, etc. Furthermore, a service (the so-called one-hour photo) has even been requested to return it to the customer a few hours after receipt. Under these circumstances, the above points have raised even greater problems.

Another problem is that bleach stain may be caused in a photosensitive material if only a small replenishment of a bleach solution is made, resulting in increased accumulation of color developing components in a bleach solution as explained above. The current state is that the bleach stain problem has become more and more acute with a photo lab with a small processing volume, for example, the new compact photo lab has a poor replenishment rate of the bleach solution with increased evaporation volume.

Summary of the invention

An object of the invention is to provide a method for processing a silver halide color photographic light-sensitive material with a fast bleaching step and low to provide refills.

Another object of this invention is to provide a method for processing a silver halide color photographic light-sensitive material which exhibits excellent silver bleaching efficiency and improved production of leuco cyan dyes.

Another object of this invention is to provide a method of processing a silver halide color photographic light-sensitive material with an improvement in the generation of bleach spots even in a compact process with little refilling.

Another object of this invention is to provide a method for processing a silver halide color photographic light-sensitive material with less complicated procedure and less control of the processing solutions.

The present inventors have made diligent studies to solve the above problems and found that the above objects of this invention can be achieved by a method for processing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer, which comprises image-wise exposure and subsequent treatment in at least a color development step and a bleaching step, wherein a bleaching solution used in the bleaching step contains at least one ferric complex of an organic acid; and wherein the bleaching solution contains at least one organic acid and the bleaching solution is replenished, characterized in that a silver halide color photographic light-sensitive material is processed, wherein at least one layer of the silver halide emulsion layer contains at least one magenta coupler having the general formula (M)

wherein Z is a non-metal atom group required to form a nitrogen-containing heterocyclic ring, the ring optionally having a substituent; X is a hydrogen atom or a substituent eliminable by a reaction with an oxidized product of a color developing agent; and R is a hydrogen atom or a substituent; that the organic acid is contained in a range of not more than 10 mol% of the content of the ferric complex of the organic acid contained in the bleaching solution; and that the replenishment amount in the bleaching step is 30 ml to 300 ml per 1 m² of the silver halide color photographic material.

A preferred subject of this invention is the embodiment in which the bleaching solution in this invention contains at least one of the compounds of the general formula (I)-(IX) as listed below.

General formula (I):

In the formula, Q is a group of atoms necessary for the formation of the nitrogen-containing heterocyclic ring (including the ring condensed with an unsaturated 5- to 6-membered ring); and R₁ is 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 hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.

A represents

or an n₁-valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring); X represents =S, =O or =NR''. Here, R and R' each have the same meaning as defined for R₂ and R₃; X' has the same meaning as defined for X; Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, an alkyl group or

; M is a divalent metal atom;

R'' is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring) or an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6. B is an alkylene group having 1 to 6 carbon atoms; Y is -N< or -CH<; R₄ and R₅ each have the same meaning as defined for R₂ and R₃; with the proviso that R₅ and R₅ each 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 the compound having the enol form 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 hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B₁-SZ₁; with the proviso that R₆ and R₇ may be combined to form a ring. Y₁ represents N- or CH-; B₁ is an alkylene group having 1 to 6 carbon atoms; Z₁ is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group or

; and n 7 is an integer from 1 to 6.

General formula (IV):

In the formula, R�8 and R�9 each represent

and R₁₀ is an alkyl group or -(CH₂)n8SO⁻ (provided that 1 represents zero when R₁₀ is -(CH₂)-n8SO⁻, or 1 when it is an alkyl group). G⁻ is an anion; and n8 is an integer from 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; with the proviso that Q' has the same meaning as defined for Q₁.

General formula (VI):

In the formula, D�1, D�2, D�3 and D�4 each represent a simple Bonding arm, an alkylene group having 1 to 8 carbon atoms or a vinylene group; and q1, q2, q3 and q4 are each an integer 0, 1 or 2. The ring formed together with a sulfur atom may be further condensed with a saturated or unsaturated 5- to 6-membered ring, with the exception of elemental sulfur;

General Formula VI-13:

General formula (VII):

In the formula, X2; -COOM', -OH, -SO₃M', -CONH₂, -SO₂NH₂, -NH₂, -SH, -CN, -CO₂R₁₆, -SO₂R₁₆, - OR₁₆, -NR₁₆R₁₇, -SR₁₆, -SO₃R₁₆, -NHCOR₁₆, -NHSO₂R₁₆, -OCOR₁₆ or -SO₂R₁₆; Y2; means

or a hydrogen atom; and m9 and n9 are each an integer of 1 to 10. R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₇ and R₁₈ are each a hydrogen atom, a lower alkyl group, an acyl group or

R₁₆ is a lower alkyl group; R₁₇ represents -NR₂₀R₂₁, -OR₂₂ or -SR₂₂; R₂₀ and R₂₁ are each a hydrogen atom or a lower alkyl group; and R₂₂ is a group of atoms, which is necessary for the formation of a ring in combination with R₁₈. R₂₀ or R₁₁ may be combined with R₁₈ to form a ring. M' is a hydrogen atom or a cation.

General formula (VIII):

In the formula, Ar is a divalent aryl group or a divalent organic group formed by combining an aryl group with an oxygen atom and/or an alkylene group; B2 and B3 are each a lower alkylene group; R23, R24, R25 and R26 each represent a hydroxy-substituted lower alkyl group; and x and y are each 0 or 1. G' is an anion; and z is 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 carboxy group.

The compounds represented by the general formulas (I) to (IX) respectively and preferably used in this invention are compounds generally used as bleaching accelerators, which are hereinafter referred to as the bleaching accelerators of this invention.

Typical examples of the bleaching accelerators of this invention may include, for example, but are not limited to, the following.

Another preferred object of this invention is the object in which at least one layer of the light-sensitive silver halide color photographic material contains 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 is an unsubstituted or substituted aryl group; and Z is a hydrogen atom or a group eliminable by a coupling reaction with an oxidizing product of an N-hydroxyalkyl-substituted-p-phenylenediamine derivative as a developing agent).

Another preferred object of this invention is the object wherein the magenta coupler of formula (M) has at least one aromatic sulfonyl group represented by the following formula in its molecular structure:

Formula (A)

wherein R₁ represents an aliphatic group, an aryl group or a heterocyclic group; m is an integer 1 or 2, R₁ may be the same or different when m is 2; R₂ is an aliphatic group, an aryl group or a heterocyclic group or

wherein R₃ and R₄ each represent a hydrogen atom, an aliphatic group or an aryl group.

Detailed description of the invention

The invention is explained more fully below.

In the regeneration of a bleaching solution, a large amount of a free organic acid has been included as a stabilizer to prevent precipitation and decomposition caused by the ferric complex of the organic acid upon aeration.

It has now been found by the present inventors that the above-mentioned object of this invention can be achieved by maintaining the concentration of a free organic acid in a bleaching solution at a molar percentage of not more than 10 mol% to the ferric complex of the organic acid as a bleaching agent in a photosensitive material.

In adapting a compact process with little replenishment, the contact time with air becomes longer due to the prolonged remaining time of a bleaching solution in the storage tank etc., or due to increased aeration, and it has been found that the precipitation or decomposition caused by the ferric complex of the organic acid can be improved even if substantial aeration is carried out. Moreover, it is surprising that the bleaching stains caused by color developing components, i.e., oxidation products of color developing agents, accumulated in a bleaching solution can be reduced.

The amount of the existing bleaching solution to be replenished is 30 ml to 300 ml per 1 m² of a silver halide color photographic light-sensitive material, more preferably 40 ml to 250 ml, most preferably 50 ml to 200 ml.

The organic acid or the organic cation capable of forming the iron(III) complex of the organic acid Acid may suitably be an aminocarboxylic acid compound or an amino acid compound, namely the amino compound having at least two or more carboxy groups or the amino compound having at least two or more phosphonic acid groups; preferably those compounds having the following general formulae (XII) and (XIII).

In the above formula, E is a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R₈₃OR₈₃OR₈₃- or -R₈₃ZR₈₃-, Z is N-R₈₃-A₆ or N-A₆, R₇₇ 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.

Preferred illustrative compounds having the general formula (XII) and (XIII) are listed below.

Explanatory connections

(XII-1) Ethylenediaminetetraacetic acid

(XII-2) Diethylenetriaminepentaacetic acid

(XII-3) Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid

(XII-4) Propylenediaminetetraacetic acid

(XII-5) Triethylenetetraminehexaacetic acid

(XII-6) Cyclohexanediaminetetraacetic acid

(XII-7) 1,2-Diaminopropanetetraacetic acid

(XII-8) 1,3-Diaminopropan-2-ol-tetraacetic acid

(XII-9) Ethyl ether diaminetetraacetic acid

(XII-10) Glycol ether diaminetetraacetic acid

(XII-11) Ethylenediaminetetrapropionic acid

(XII-12) Phenylenediaminetetraacetic acid

(XII-13) Ethylenediaminetetraacetic acid sodium salt

(XII-14) Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt

(XII-15) Ethylenediaminetetraacetic acid tetrasodium salt

(XII-16) Diethylenetriaminepentaacetic acid pentasodium salt

(XII-17) Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt

(XII-18) Propylenediaminetetraacetic acid sodium salt

(XII-19) Ethylenediaminetetramethylenephosphonic acid

(XII-20) Cyclohexanediaminetetraacetic acid sodium salt

(XII-21) Diethylenediaminepentamethylenephosphonic acid

(XII-22) Cyclohexanediaminetetramethylenephosphonic acid

(XIII-1) Nitrilotriacetic acid

(XIII-2) Iminodiacetic acid

(XIII-3) Hydroxymethylimino-di-acetic acid

(XIII-4) Nitrilotripropionic acid

(XIII-5) Nitrilotrimethylenephosphonic acid

(XIII-6) Iminodimethylenephosphonic acid

(XIII-7) Hydroxyethyl imidodimethylene phosphonic acid

(XIII-8) Nitrilotriacetic acid trisodium salt

Among these, particularly preferred compounds for the intended effects of this invention may be mentioned aminocarboxylic acid compounds and aminephosphonic acid compounds (XII-1), (XII-2), (XII-5), (XII-8), (XII-19), (XIII-1), (XIII-3) and (XIII-5).

The amount of the aminocarboxylic acid or aminophosphonic acid compounds to be added in this invention may be 10% or less of the molar concentration of the ferric complex of the organic acid coexisting in a bleaching solution, preferably 0 to 5%, more preferably 0 to 2%, in order to more effectively exhibit the present effects.

The iron(III) complex of the organic acid according to this The invention can be used as a free acid (hydrogen acid), an alkali metal salt such as sodium salt, potassium salt or lithium salt, an ammonium salt, a water-soluble amine salt such as triethanolamine salt, preferably potassium salt, sodium salt or ammonium salt. The iron(III) complexes can be used as at least one kind thereof or in combination of two or more. The amount to be used can be optionally selected and should be determined depending on the silver amount of the light-sensitive material to be processed, the composition of silver halide and the like; for example, one should use not less than 0.01 mol per 1 liter of the solution used, preferably 0.05 to 0.6 mol. In the replenisher solution, it is preferable to apply a concentration of solubility as compressed as possible for compressed low replenishment.

The effect of this invention can be more clearly exhibited and a further effect of preventing precipitation due to silver in the bleaching solution can also be expected when the bleaching solution contains at least one of the compounds represented by the general formulas (I) to (IX) as shown below, which are therefore preferably used in this invention.

General formula (I)

In the formula, Q is a group of atoms necessary for the formation of the nitrogen-containing heterocyclic ring (including the ring condensed with an unsaturated 5- to 6-membered ring); and R₁ is 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 hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.

A represents

or an n₁-valent heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring); X represents =S, =O or =NR''. Here, R and R' each have the same meaning as defined for R₂ and R₃; X' has the same meaning as defined for X; Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic radical, an alkyl group or

; M is a divalent metal atom;

R'' is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring) or an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6. B is an alkylene group having 1 to 6 carbon atoms; Y is -N< or -CH<; R₄ and R₅ each have the same meaning as defined for R₂ and R₃; provided that R₄ and R₅ each 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 the compound having the enol form 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 hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B₁-SZ₁; with the proviso that R₆ and R₇ may be combined to form a ring. Y₁ represents >N- or >CH-; B₁ is an alkylene group having 1 to 6 carbon atoms; Z₁ is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group or

; and n7 is an integer from 1 to 6.

General formula (IV):

In the formula, R�8 and R�9 each represent

and R₁₀ is an alkyl group or -(CH₂)n8SO⁻ (provided that 1 represents zero when R₁₀ is -(CH₂)n8SO⁻, or 1 when it is an alkyl group). G⁻ is an anion; and n8 is an integer from 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 which is hydrogenated with an unsaturated or saturated 5- to 6-membered ring condensed); and R₁₁ is a hydrogen atom, an alkali metal atom,

or an alkyl group; with the proviso that Q' has the same meaning as defined for Q₁.

General formula (VI):

In the formula, D1, D2, D3 and D4 each represent a simple bonding arm, an alkylene group having 1 to 8 carbon atoms, or a vinylene group; and q1, q2, q3 and q4 are each 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, excluding elemental sulfur;

General Formula VI-13:

General formula (VII):

In the formula, X2; -COOM', -OH, -SO₃M', -CONH₂, -SO₂NH₂, -NH₂, -SH, -CN, -CO₂R₁₆, -SO₂R₁₆, - OR₁₆, -NR₁₆R₁₇, -SR₁₆, -SO₃R₁₆, -NHCOR₁₆, -NHSO₂R₁₆, -OCOR₁₆ or -SO₂R₁₆; Y2; means

or a hydrogen atom; and m9 and n9 are each an integer of 1 to 10. R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₇ and R₁₈ are each a hydrogen atom, a lower alkyl group, an acyl group or

R₁₆ is a lower alkyl group; R₁₇ represents -NR₂�0R₂₁, -OR₂₂ or -SR₂₂; R₂₀ and R₂₁ are each a hydrogen atom or a lower alkyl group; and R₂₂ is a group of atoms required for forming a ring in combination with R₁₈. R₂₀ or R₁₁ may be combined with R₁₈ to form a ring. M' is a hydrogen atom or a cation.

General formula (VIII):

In the formula, Ar is a divalent aryl group or a divalent organic group formed by combining an aryl group with an oxygen atom and/or an alkylene group; B2 and B3 are each a lower alkylene group; R23, R24, R25 and R26 each represent a hydroxy-substituted lower alkyl group; and x and y are each 0 or 1. G' is an anion; and z is 0, 1 or 2.

General formula (IX):

In the formula, R₂�9 and R₃�0 are each 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 carboxy group.

The compounds represented by the general formulas (I) to (IX) respectively and preferably used in this invention are compounds generally used as bleaching accelerators, which are hereinafter referred to as the bleaching accelerators of this invention.

Typical examples of the bleaching accelerators of this invention may include, but are not limited to, the following.

(III-38)

HOOC-H₂C-S-S-CH₂-COOH

(III-39)

HOOC-H₂CH₂CSS-CH₂-CH₂-COOH

In addition to the bleaching accelerators of this invention as exemplified above, similarly usable compounds may also include the exemplified compounds mentioned in JP-A-263568/1985 on page 51 to page 115 of the specification, i.e. the compounds No. I-2, I-4 to -7, I-9 to -13, I-16 to -21, I-23, I-24, I- 26, I-27, I-30 to -36, I-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 -99, II-101, II-102, II-104 to -110, II-112 to -119, II-121 to 124, II-126, II-128 to -144, I1-146, II-148 to -155, II-157, III-4, III-6 to -8, III-10, III-11, III-13, III-15 to -18, III-20, III-22, III-23, III-25, III-27, III-29 to -32, III- 35, III-36, IV-3, IV-4, V-3 to -6, V-8 to -14, V-16 to -38, V-40 to -42, V-44 to -46, V-48 to -66, V-68 to -70, V-72 to -74, V-76 to -79, V-81, V-82, V-84 to -100, V-102 to -108, V-110, V-112, V-113, V-116 to -119, V-121 to -123, V-125 to -130, V-132 to -144, V-146 to -162, V-164 to -174, V-176 to -184, VI-4, VI-7, VI-10, VI-12, VI-13, VI-16, VI-19, VI-21, VI-22, VI-25, VI-27 to -34, VI-36, VII-3, VII-6, VII-13, VII-19, VII-20, etc.

The compounds of the general formulas (I) to (IX) may be used alone or in combination with two or more of them, and an amount of the bleaching accelerator to be added to the bleaching solution is usually in the range of 0.01 to 100 g per 1 liter of the processing solution in order to obtain favorable results. In general, however, the bleaching accelerating effect is small if the amount added is too small, while if the amount added is too large above the required level, precipitates may form and staining may occur on the silver halide color photographic light-sensitive material to be processed. Therefore, 0.05 to 50 g per 1 liter of the processing solution is preferable, more preferably 0.05 to 15 g per 1 liter of the processing solution.

The present compounds having the above general formulae (I) to (IX), when added to the bleaching solution, may be added as such and dissolved, but are generally added after previously dissolving in water, an alkali, an organic acid, etc., and if necessary, they may be added dissolved in an organic solvent such as methanol, ethanol or acetone so as not to exert any influence on their bleaching effect and the effects highlighted above.

The processing time for bleaching a silver halide color photographic light-sensitive material with the given bleaching solution is preferably short in order to exhibit the given effects more effectively. The preferred bleaching time is six minutes or less, more preferably it is four minutes or less.

The given bleaching solution can be used at a pH of 0.2 to 9.5, preferably 2.0 to 8.0, more preferably 4.0 to 7.0. The processing temperature may be 80°C or less, desirably 55°C or less for preventing evaporation and others.

In general, the given bleaching solution may contain a halide such as ammonium bromide and the like.

The given bleaching solution may also contain a pH buffering agent alone or in combination with two or more thereof, wherein the buffering agent may consist of various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, acetic acid, sodium acetate, ammonium hydroxide and the like. Furthermore, various brightening agents, defoaming agents, surfactants, mildew inhibitors and the like may be incorporated into the bleaching solution.

The aromatic primary amine color developing agent which can preferably be used in the existing color developing solution may contain various agents which can be widely used in a variety of color photographic processing. Such developing agents may include aminophenol and p-phenylenediamine type derivatives.

These compounds can generally be used in the form of a salt, e.g. the hydrochloride or the sulfate, which stabilize better than the free form. They can usually be used at a concentration of from about 0.1 g to about 50 g per 1 liter of color developer, more preferably from about 1 g to about 1.5 g per 1 liter of developer.

Developers of the aminophenol type can be mentioned as for example o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-amino-1,4-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 agents containing an amino group having at least one water-soluble group, and the compounds represented by the general formula [X] are particularly preferred.

In this formula, R₁₃ is a hydrogen atom, a halogen atom or an alkyl group, the 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, the alkyl or aryl group being optionally substituted. In the case of alkyl groups, an alkyl group substituted with an aryl group is preferred. At least one of R₁₄ and R₁₅ is an alkyl group, which is 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 with -[-(CH₂)qO-]pR₁₆, the alkyl group being optionally further substituted. R₁₆ is a hydrogen atom or an alkyl group having a straight or branched chain of 1 to 5 carbon atoms, and p and q are each an integer of 1 to 5.

Examples of the compounds represented by the above general formula [X] are given below, but the compounds of the present invention are not limited to these.

[Example connection]

The p-phenylenediamine derivatives represented by the above general formula (X) can be used as salts with an organic or inorganic acid, and they can be used, for example, as hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, oxalate, benzenedisulfonate and the like.

The color developing solution used in this invention may optionally further contain various components which are conventionally used, 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 thickening agent; a development accelerator; and the like.

Next, the cyan coupler according to this invention will be described.

The cyan coupler of this invention can be represented by the formula (C) as shown below.

wherein R₂₁ 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, any of the groups 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 a 5- to 7-membered group (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 having a 5- or 6-membered ring containing 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms (for example a furyl group, a thienyl group, a benzothiazolyl group, etc.).

In R₂₁ a desired substituent can 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, the dimethylcarbamoyl group, phenylcarbamoyl group, etc.), an oxycarbonyl group (for example, ethoxycarbonyl, phenoxycarbonyl, etc.), an acyl group (for example, example acetyl, benzoyl, etc.), a hetero ring (for example a pyridyl group, a pyrazolyl group, etc.), an alkoxy group, an aryloxy group, an acyloxy group, etc.).

R₂₁ is a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula (C), and a cyan dye is formed from this cyan coupler. Preferably, it is an alkyl group having 4 to 30 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group or 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 the formula (C), R₂₄ represents a substituted or unsubstituted aryl group (particularly preferred is a phenyl group). The substituent in the case where the aryl group has a substituent may be at least one of the substituents selected from SO₂ R₂₅, a halogen atom (such as fluorine, chlorine, bromine, etc.), -CF₃, -NO₂, -CN,

Herein, R₂₅ represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each 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 a heptadecenyl group), a cycloalkyl group, preferably a 5- to 7-membered group (for example, cyclohexyl, etc.), an aryl group (for example, a phenyl group, a tolyl group, a naphthyl group, etc.); and R₂₆ is a hydrogen atom or the group represented by R₂₅.

A preferred compound of the cyan coupler of this invention represented by the formula (C) is a compound in which R24 is a substituted or unsubstituted phenyl group, and the substituent for the phenyl group is cyano, nitro, -SO2R27 (R27 is an alkyl group), a halogen atom or trifluoromethyl.

Preferred examples of the ballast group represented by R₂₁ include a group represented by the formula (C-1) shown below.

Formula (C-1):

In the formula, J is an oxygen atom or a sulfonyl group; K is an integer from 0 to 4; 1 means 0 or 1; and R₂₉ which is present two or more times when K comprises two or more may be the same or different; R₂₈ is a straight-chain or branched alkylene group having 1 to 20 carbon atoms and substituted with an aryl group, etc.; and R₂₉ is is a monovalent group, preferably a hydrogen atom, a halogen atom (for example chlorine, bromine, etc.), an alkyl group, preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms (for example any of the groups methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, 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 any of the groups methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), an aryloxy group (for example a phenoxy group), a hydroxy group, an acyloxy group, preferably an alkylcarbonyloxy group, an arylcarbonyloxy group (for example an acetoxy group and a benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably a straight-chain 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-chain 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 with 1 to 20 carbon atoms or a phenylaminosulfonyl group, etc.

In the formula (C), Z represents a hydrogen atom or a group eliminable by a coupling reaction with an oxidized product of the N-hydroxyalkyl-substituted-p-phenylenediamine derivative as a 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 carbamoyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonamide group, etc., and more specifically, examples may include those described in US-A-3741563, JP-A-37425/1972, JP-B-34894/1973, JP-A-10135/1975, JP-A-117422/1975, JP-A-130441/1975, JP-A-108841/1976, JP-A- 120343/1975, JP-A-18315/1977, JP-A-105226/1978, JP-A- 14736/1979, JP-A-48237/1979, JP-A-32071/1980, JP-A-65957/1980, JP-A-1938/1981, JP-A-12643/1981, JP-A-27147/1981, JP-A- 146050/1984, JP-A-166956/1984, JP-A-24547/1985, JP-A- 35731/1985 and JP-A-37557/1985 etc.

Specific exemplary compounds for the cyan coupler of this invention represented by formula (C) are listed below, but are not limited to them.

These cyan couplers of the present invention can be prepared by known methods, for example synthesis methods as described in US-A-3222176, US-A-3446622 and US-A-3996253; GB-A-1011940; JP-A-21139/1972, JP-A-65134/1981, JP-A-204543/1982 and JP-A-204544/1982; JP-A- 33250/1983, JP-A-33248/1983, JP-A-33249/1983, JP-A-33251/1983, JP-A-33252/1983 and JP-A-31334/1983; JP-A-24547/1985, JP-A- 35731/1985 and JP-A-37557/1985; etc.

The cyan couplers of the present invention represented by the formula (C) may be used alone or as a combination of two or more thereof. When the cyan couplers of the present invention are contained in a silver halide emulsion layer, the amount thereof is usually about 0.005 to 2 mol, preferably 0.01 to 1 mol, per 1 mol of silver halide contained in the silver halide emulsion layer.

The photographic material for carrying out the process of the present invention is one which contains, in at least one layer of its silver halide emulsion layer, a magenta coupler represented by the formula (M).

When the substituent (e.g. R, R₁ to R₈) attached to the heterocyclic ring in the formula (M) and the formulas (MI) to (M-VI) as described below is a radical of the formula

(wherein R'', X and Z'' have the same meaning as R, X and Z in the formula (M)), the so-called bis-form of the coupler is formed, which is of course included in the present invention. The ring formed by Z, Z', Z'' and Z₁ as described below can also be condensed with another ring (e.g. with a 5- to 7-membered cycloalkene). For example, R₅ and R₆ in the Formula (M-IV), R₇ and R₈ in Formula (MV) may be linked to form a ring (e.g., a 5- to 7-membered ring).

The compounds represented by formula (M) can also be specifically represented by the following formulas (M-I) to (M-VI).

Formula (MI)

Formula (M-II)

Formula (M-III)

Formula (M-IV)

Formula (MV)

Formula (M-VI)

In the above formulas (M-I) to (M-VI), R₁ to R₈ and X have the same meaning as R and X above.

Of the compounds represented by the formula (M), preferred are those represented by the following formula (M-VII).

wherein R₁, X and Z₁ have the same meaning as R, X and Z in the formula (M).

Of the magenta couplers represented by formulas (M-I) to (M-VI), the magenta couplers represented by formula (M-I) are particularly preferred.

For example, to describe the substituents on the heterocyclic ring in the formula (M) and (M-I) to (M-VII), R in the formula (M) and R₁ in the formulas (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: the root atom directly bonded to the heterocyclic ring is a carbon atom,

Condition 2: only one hydrogen atom is bonded to the carbon atom, or no hydrogen atom is bonded to it, and

Condition 3: the bonds between the root atom and the neighbouring atoms are all single bonds.

Of the substituents R and R₁ on the above heterocyclic ring, the most preferred are those represented by the formula (M-VIII) as shown below:

In the above formula, R�9, R₁₀ and R₁₁ each represent 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 residual group of a spiro compound, a residual group of a bridging hydrocarbon compound, an alkoxy group, an aryloxy group, a heterocyclic-oxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino 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, a alkylthio group, an arylthio group or a heterocyclic-thio group. At least two of R�9;, R₁₀ and R₁₁ are not hydrogen atoms at the same time.

Furthermore, at least two of R₉, R₁₀ and R₁₁, for example, R₉ and R₁₀, are bonded together to form a saturated or unsaturated ring (e.g., a cycloalkane ring, cycloalkene ring or heterocyclic ring), and further to form a residual group of a bridging hydrocarbon compound by bonding R₁₁ to this ring.

The groups represented by R9, R10 and R11 may have substituents, and examples of the groups represented by R9, R10 and R11 and the substituents carried by these groups may include examples of the substituents represented by R in the above formula (M) and substituents carried by those substituents.

Examples of the ring formed by bonding between R₉ and R₁₀, the residual group of the bridging hydrocarbon compound formed by R₉, R₁₀ and R₁₁, and the substituents carried by those include cycloalkyl, cycloalkenyl and heterocyclic groups as described for the Substituents on R in the above formula (M) and their substituents were mentioned.

Of the groups of formula (M-VIII) the following are preferred:

(i) the case where two of R�9, R₁₀ and R₁₁ are alkyl groups and

(ii) the case where one of R9, R10 and R11, for example R11, is a hydrogen atom and the other two R9 and R10 are joined together to the root carbon atom to form a cycloalkyl group.

Further preferred in (i) is the case where two of R9, R10 and R11 are alkyl groups and the other is a hydrogen atom or an alkyl group.

The above-mentioned alkyl and cycloalkyl groups may further have substituents, and examples of these alkyl, cycloalkyl and the substituents thereof may include those such as alkyl, cycloalkyl and substituents thereof as previously mentioned for the substituents on R in the formula (M) and their substituents.

The magenta coupler represented by formula (M) may include the specific compounds numbered below.

Magenta couplers for photography combined with the magenta coupler of this invention may include pyrazolone type, pyrazolinobenzimidazole type and indazolone type compounds, etc. Pyrazolone type magenta couplers may include compounds disclosed in US-A- 2600788, US-A-3062653, US-A-3127269, US-A-3311476, US-A- 3419391, US-A-3519429, US-A-3558318, US-A-3684514 and US-A- 3888680, JP-A-29639/1974, JP-A-111631/1974, JP-A-129538/1974 and JP-A-13041/1975, JP-B-478167/1978, JP-B-10491/1979 and JP-B-30615/1980. As the non-diffusion magenta color coupler, there can be generally used the compounds arylazo-substituted at the coupling position of a colorless magenta coupler, which include, for example, the compounds disclosed in US-A-2801171, US-A-2983608, US-A-3005712 and US-A-3684514, GB-A-937621, JP-A-123625/1974 and JP-A-31448/1974.

Magenta color couplers of the type in which a dye can flow into a processing solution by reaction with an oxidized product of a developing agent, as disclosed in US-A-3419391, may also be used.

In the silver halide photographic light-sensitive material used for the processing method of this compound, there may preferably be used a pyrazola sol type magenta coupler having at least one aromatic sulfonyl group in the molecular structure represented by the formula (A)

The pyrazolazole type magenta coupler having at least one aromatic sulfonyl group represented by the formula (A) in the molecular structure and used for this invention may preferably be a magenta coupler represented by the following formula (M).

wherein Z represents non-metal atoms necessary for forming a nitrogen-containing heterocyclic ring, the ring formed by Z may have a substituent; X is a hydrogen atom or a group eliminable by reaction with an oxidized product of a color developing agent; R is 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 the substituents has the group represented by the formula (A).

The aromatic sulfonyl group represented by formula (A) is described in detail below Formula (A):

In the formula, R₁ represents an aliphatic group, an aryl group or a heterocyclic group; m is an integer 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, an aliphatic group or an aryl group).

To describe R₁ and R₂ of the formula (A) 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. These aliphatic groups may include those having a substituent, wherein the substituent may include groups other than hydrogen mentioned for R above. The aryl group may include, for example, a phenyl group, a naphthalene group, etc., and it may include those having a substituent, the substituent may include 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 atom 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 piperidine group, a morpholine group, a benzimidazolyl group, a triazolyl group, a triazine group, etc.). It may include those having a substituent, the substituent may include groups other than hydrogen mentioned for the above R.

The group

may include a di-substituted amino group, substituted with an aliphatic group or an aryl group.

Of the sulfonyl group represented by formula (A), preferred is the compound represented by the following formula

In the formula, R₁₂ and R₁₃ are a group having the same meaning as defined for R₁ and R₂ in the formula (A).

More preferred is the compound wherein R₁₂ is an alkyl group. Especially preferred is the compound wherein R₁₃ is an aryl group substituted with an alkoxy group.

Typical examples of the magenta coupler used in this invention include, but are not limited to, those listed below.

The pyrazolazole type magenta coupler of the present invention, which has at least one aromatic sulfonyl group represented by the formula (A) in the molecular structure, can be synthesized by referring to Journal of the Chemical Society, Perkin I (1977), 2047-2052, US-A-3725067, JP-A- 99437/1984, JP-A-42045/1983, JP-A-162548/1984, JP-A- 171956/1984, JP-A-33552/1985, JP-A-43659/1985, JP-A-172982/1985 and JP-A-190779/1985, etc.

The pyrazolazole type magenta coupler of this invention may generally be used in the range of 1·10⁻³ mol to 1.5 mol, preferably 1·10⁻² mol to 1 mol, per mol of silver halide.

The pyrazolazole type magenta coupler of this invention can be used in combination with other types of magenta couplers.

The pyrazoazole type magenta couplers 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 point solvent and/or a water-soluble organic solvent, and effect emulsification dispersion of the solution in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. A step of removing the dispersing solution may be inserted, or at the same time of dispersion, the low-boiling point organic solvent.

As a further preferred object of this invention, it has been found that the object of this invention can be more effectively achieved by incorporating into the silver halide photographic light-sensitive material at least one of the compounds having the following general formula (XI).

In this formula, Z₁₁ and Z₂₁ each represent a group of atoms necessary to form a benzene ring or a naphthalene ring condensed with an oxazole ring. R₄₁ and R₄₂ each represent an alkyl group, an alkenyl group or an aryl group, R₄₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X₁⁻ is an anion, and n is 1 or 0.

The definitions of the general formula [XI] are explained in detail.

In the formula, Z₁₁ and Z₂₁ each represent a group of atoms required for forming a benzene ring or a naphthalene ring condensed with an oxazole ring. The heterocyclic ring to be formed may be substituted with a substituent of various kinds, and these substituents may preferably include a halogen atom, an aryl group, an alkenyl group, an alkyl group and an alkoxy group. More preferred substituents are a halogen atom, a phenyl group and a methoxy group, and the most preferred substituent is a phenyl group.

A preferred object is that both Z₁₁ and Z₂₁ represent benzene rings each fused with oxazole rings, 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 they are preferably an alkyl group. More preferably, R₄₁ and R₄₂ each represent an alkyl group substituted with a carboxy group or a sulfo group, and most preferably a sulfoalkyl group having 1 to 4 carbon atoms. Most preferably, they are each a sulfoethyl group. R₄₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is preferably a hydrogen atom or an ethyl group. X₁⊃min; represents an anion; and n represents 0 or 1.

The sensitizing dye used in this invention represented by the general formula (XI) can also be used in combination with other sensitizing dyes as a so-called supersensitizing combination. In such a case, the respective sensitizing dyes can be dissolved in solvents of the same or different types, and these solutions can be mixed before being added to an emulsion or added separately to the emulsion. When they are added separately, the order and time interval can be arbitrarily determined depending on the purpose.

Specific examples of the sensitizing dye represented by the general formula (XI) are listed below, but the sensitizing dyes used in this invention are not limited to these compounds. sensitizing dye

The sensitizing dye having the above formula (XI) may be added to an emulsion at any point during the preparation of the emulsion, and preferably during or after chemical ripening. The amount of the dye to be added may preferably be 2 × 10⁻⁶ mol to 1 × 10⁻³ mol per 1 mol of the silver halide, more preferably 5 × 10⁻⁶ mol to 5 × 10⁻⁴ mol per 1 mol of the halide.

As the silver halide emulsion that can be used in this invention, any emulsion using any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide or silver chloroiodobromide can be used. As the protective colloid for these silver halides, natural products such as gelatin and similar or various synthetic products can be used. The silver halide emulsion can also contain usual photographic additives such as a stabilizer, a sensitizer, a hardening agent, a sensitizing dye, a surfactant and others.

The processing method of this invention can be applicable to silver halide color photographic light-sensitive materials such as color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movie films, color reversal film for TV or color reversal paper. In particular, the present method is most suitable for processing a highly light-sensitive silver halide color photographic material containing silver iodobromide or chloroiodobromide containing 0.1 mol% or more of silver iodide and having a total coating amount of silver of not less than 20 mg/dm².

Comparison example 1

An antihalation layer and a gelatin layer were coated on a triacetate film base, and over these were coated 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 were applied so that a total silver amount of 60 mg per 100 cm² was obtained. The above emulsion layers individually contained a mol% of silver iodide of about 4.5% of the silver iodobromide, while the following yellow coupler (Y-1) was used 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'-I) for the red-sensitive silver halide emulsion layer Yellow coupler (Y-1)

Magenta coupler (M'-1)

Cyan coupler (C'-1)

Furthermore, such conventional additives as a high boiling solvent, a sensitizing dye, a hardening agent, a spreader and the like can be used. The thus prepared Color negative films were exposed according to conventional procedures and then subjected to a process sequence according to the stages of the development process listed below. Processing stage Processing temperature Processing time 1. Colour development 2. Bleaching 3. Fixing 4. Washing 5. Stabilisation 6. Drying

The color developing solution, bleaching solution, fixing solution and stabilizing solution described below were used.

[Color developing solution]

Potassium carbonate 30 g

Sodium hydrogen carbonate 2.5 g

Potassium sulphite 5.0 g

Sodium bromide 1.3 g

Potassium iodide 2 mg

Hydroxylamine sulfate 2.5 g

Sodium chloride 0.6 g

Diethylenetriamine pentasodium acetate 2.5 g

4-Amino-3-methyl-N-(β-hydroxyethyl)-aniline sulfate 4.8 g

Potassium hydroxide 1.2 g

Water was added until the volume reached 1 liter and the pH was adjusted to 10.06 with potassium hydroxide or 20% sulfuric acid.

[Bleaching solution and bleach refill]

Ethylenediaminetetraacetate(III) complex 0.35 mol

Ethylenediaminetetraacetic acid 0-0.1 mol

(as shown in Table 1 below)

Ammonium bromide 140 g

aqueous ammonia (28% solution) 10 ml

Water was added until the volume reached 1 liter and the pH was adjusted to 6.0 with acetic acid and with aqueous ammonia.

[Fixing solution and fixer refill]

Ammonium thiosulfate 170 g

Ammonium sulphite 16 g

It was filled with water to 1 liter volume and the pH was adjusted to 7.0 with acetic acid and aqueous ammonia.

[Stabilizing solution and stabilizing refiller]

Formalin (37% aqueous solution) 2 ml

Conidax 5 ml

(available from Konishiroku Photo Industry Co., Ltd.) Water was added until the volume reached 1 liter.

[Color Development Replenisher]

Potassium carbonate 35 g

Sodium hydrogen carbonate 3.0 g

Potassium sulphite 7.0 g

Sodium bromide 0.9 g

Hydroxylamine sulfate 3.1 g

Sodium diethylenetriamine pentaacetate 3.2 g

3-Amino-3-methyl-N-(β-hydroxyethyl)-aniline sulfate 5.4 g

Potassium hydroxide 2.0 g

Water was added until the volume reached 1 liter and the pH was adjusted to 10.12 with potassium hydroxide or 20% sulfuric acid.

The bleach replenisher, fixer replenisher and stabilizer replenisher were used with the same compositions as the corresponding tank solutions. Also, the concentrations of ethylenediaminetetraacetic acid as an example of the organic acid included in the bleach solution varied according to the following Table 1.

The color development refiller was added to the color development solution at 1.5 l per 1 m² of the color negative film and the fixer replenisher was added to the fixer at 1 l per 1 m² of the color negative film. Likewise, the stabilizer replenisher was added at 1 l per 1 m² of the color negative film and the wash water was allowed to flow at 15 l per 1 m² of the film. The bleach replenisher was added at a replenishment volume as shown in Table 1 below.

A continuous process was performed on 50 m² of a color negative film while the pH of the bleaching solution was precisely adjusted to pH 6.0. The processed sample after the process was measured for the density of cyan dye in the maximum density band by means of "Sakura" photoelectric densitometer PDA-65 (available from Konishiroku Photo Industry Co., Ltd.). Also, the recoloring property was determined from the difference in cyan dye density between the sample and the sample retreated with prussiate. A residual silver amount in the maximum density band was measured by the X-ray fluorescence method. The above results are summarized in Table 1. (EDTA = ethylenediaminetetraacetic acid) Table 1 Refill quantity per color negative film Conc. of (ratio to ethylenediaminetetraacetate) -iron complex Cyan dye (recoloring property) Residual silver amount

From the results of Table 1 above, it is apparent that the recoloring property of the cyan dye and the desilvering property differ greatly from each other when the replenishment amount of the bleaching solution is reduced to not more than 300 ml per 1 m² of the negative color film; however, it is understood that the bleaching solution having the concentration of ethylenediaminetetraacetic acid as an example of the organic acids included in the bleaching solution within the scope of this invention shows extremely slight deterioration in both the recoloring and desilvering properties even when the replenishment amount of the bleaching solution is greatly reduced.

Example 2

An antihalation layer and a gelatin layer were coated on a triacetate film base, and over these were coated 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 the total silver amount was 72 mg per 100 cm². The above-mentioned emulsion layers individually contained a mole percentage of silver iodide of about 4.3% silver iodobromide, while the yellow coupler (Y-1) as used in Comparative Example 1 was used for the blue-sensitive silver halide emulsion layer, the exemplified magenta coupler (M-5) for the green-sensitive silver halide emulsion layer, and the cyan coupler (C'-1) as used in Comparative Example 1 was used for the red-sensitive silver halide emulsion layer.

Furthermore, such conventional additives as a high-boiling solvent, a sensitizing dye, a hardening agent, a spreading agent and the like were used where appropriate. The color negative film produced in this way was exposed according to conventional methods and then subjected to a process sequence following the same development processing steps. as in Comparative Example 1, except that the concentration of ethylenediaminetetraacetic acid as an example of the organic acids included in the bleaching solution was changed as shown in the following Table 3.

In each step, a continuous process was carried out for 40 m² of a color negative film while the pH was precisely adjusted to pH 6.0. After the processing was completed, the treated sample was left to stand at 38ºC for three days, and then the cyan dye density in the maximum density band was measured using a "Sakura" photoelectric densitometer PDA-65 (available from Konishiroku Photo Industry Co., Ltd.). The recoloring property was also determined by the difference in cyan dye density between the sample and the sample retreated with the prussia solution, while the residual silver amount in the maximum density band was measured. The results are summarized in Table 3.

EDTA=ethylenediaminetetraacetic acid Table 3 Refill quantity per color negative film Conc. of ratio to complex cyan dye (recoloring - residual silver quantity

As is apparent from the results of Table 3, where the replenishment amount of the bleaching solution was reduced to not more than 300 ml per 1 m² of the color negative film, the recoloring and desilvering properties of the cyan dye were greatly deteriorated; however, it is also seen that both the recoloring and desilvering properties can be greatly improved with the bleaching solution in which the concentration of ethylenediaminetetraacetic acid falls within the range of this invention.

Example 3

Comparative examples were made in which the magenta coupler (M-5) used for the film sample of Example 2 was replaced by the comparative magenta coupler (M'-1) as used in Example 2 and the comparative magenta coupler (M'-2) as shown below. Also, film samples of this compound were prepared in a similar manner using the exemplary magenta couplers (M-18), (M-44), (M-59), (M-7), (M-22), (M-104), (M-127) and (M-1). After storage for three days, treatment was carried out using the bleaching solution of Example 2, Test No. 44. Magenta stains in the unexposed portion were measured. As a result, the samples using the present magenta coupler showed less magenta spots than 0.04 to 0.06 in each case, compared with the magenta couplers outside the present invention.

Magenta coupler (M'-2)

Example 4

Tests were carried out using the same procedure as in Example 2, except that the exemplary Compounds (II-28), (II-144), (III-34), (III-2), (III-38), (V-71), (V-75) and (VIII-1) were applied to the bleaching solutions used in Example 2, Test Nos. 41 to 45, and the bleaching treatment times were two minutes. As a result, although the bleaching treatment time was shortened, the residual silver amount was reduced by about 15 to 20% in each case.

Example 5

Film samples were prepared by the same procedure as in Example 2, except that the exemplary compound (XI-1) or (X-4) was used for the green-sensitive silver halide emulsion layer of the film sample prepared in Example 1, and then the same tests as in Example 2 were carried out. As a result, the residual silver amount was reduced by 5 to 10% when the present bleaching solution was used.

Example 6

An antihalation layer and a gelatin layer were coated on a triacetate film base, and then coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing a yellow colloidal silver, a blue-sensitive silver halide emulsion layer and a protective layer to give a total silver amount of 65 mg per 100 cm². The above emulsion layers individually contained a silver iodide mole percentage of about 4.2% of silver iodobromide, while the above yellow coupler (Y-1) was used for the blue-sensitive silver halide emulsion layer, the above exemplary magenta coupler (M-203) for the green-sensitive silver halide emulsion layer, and the above cyan coupler (C'-1) for the red-sensitive silver halide emulsion layer. As the supersensitizer, the following (Z-1) was used.

Furthermore, such conventional additives as a high-boiling solvent, a hardening agent, a spreading agent and the like may be used if necessary. The color negative films produced in this way were exposed according to conventional methods and then subjected to a process sequence according to the development treatment steps mentioned below. Treatment stage Treatment temperature Treatment time 1. Colour development 2. Bleaching 3. Fixing 4. Washing 5. Stabilisation 6. Drying

The color developing solution, bleaching solution, fixing solution and stabilizing solution described below were used.

[Color developing solution]

Potassium carbonate 30 g

Sodium hydrogen carbonate 2.5 g

Potassium sulphite 3.6 g

Sodium bromide 1.2 g

Potassium iodide 1.5 mg

Hydroxylamine sulfate 2.5 g

Sodium chloride 0.6 g

Diethylenetriamine pentasodium acetate 2.5 g

Example compound (X-2) sulfate 4.5 g

Potassium hydroxide 1.2 g

Water was added to a volume of 1 liter and the pH was adjusted to 10.00 with potassium hydroxide or 20% Sulfuric acid is added.

[Bleaching solution and bleach refill]

Ethylenediaminetetraacetate(III)ammonium 0.35 mol

Ethylenediaminetetraacetic acid 0-0.2 mol

(as shown in Table 4 below)

Ammonium bromide 140 g

aqueous ammonia (28% solution) 10 ml.

Water was added until 1 liter volume was reached and the pH was adjusted to 5.9 with acetic acid and with aqueous ammonia.

[Fixing solution and fixer refill]

Ammonium thiosulfate 170 g

Ammonium sulphite 16 g

Water was added to make up to 1 liter volume and the pH was adjusted to 7.0 with acetic acid and aqueous ammonia.

[Stabilizing solution and stabilizing refiller]

Formalin (37% aqueous solution) 2 ml

Konidax (available from Konishiroku Photo Industry Co., Ltd.) 5 ml

Water filled up to 1 liter volume

[Color Development Replenisher]

Potassium carbonate 35 g

Sodium hydrogen carbonate 3.0 g

Potassium sulphite 4.0 g

Sodium bromide 0.9 g

Hydroxylamine sulfate 3.1 g

Sodium diethylenediamine pentaacetate 3.2 g

Example compound (X-2) sulfate 5.4 g

Potassium hydroxide 2.0 g

Water was added to make up to 1 liter and the pH was adjusted to 10.12 with potassium hydroxide or 20% sulfuric acid.

The bleach replenisher, fixer replenisher and stabilizer replenisher were used with the same composition as the corresponding tank solutions. The concentrations of ethylenediaminetetraacetic acid as an example of the organic acid included in the bleaching solution was varied as shown in Table 4 below.

The color developing replenisher was used for the color developing solution at 1.5 l per 1 m² of the color negative film, and the fixing replenisher was used for the fixing bath at 1 l per 1 m² of the color negative film. Likewise, the stabilizing replenisher was used at 1 l per 1 m² of the color negative film, and the washing water was run at 15 l per 1 m² of film. The bleaching replenisher was used at a replenishment volume as shown in Table 4 below.

A continuous processing was carried out for 40 m² of a color negative film while a pH value of the bleaching solution was adjusted to pH 6.0 exactly. The processed sample after the processing was measured for the density of cyan dye in the maximum density band by means of a "Sakura" photoelectric densitometer PDA 65 (available from Konishiroko Photo Industry Co., Ltd.). Also, the recoloring property was determined from the difference in cyan dye density between the sample and the sample treated with prussiate of potassium hydroxide. The amount of residual silver in the maximum density band was measured by the X-ray fluorescence method. The above results are shown in Table 4. Table 4 Refill quantity per color negative film Conc. of (ratio to cyan dye (recoloring property) Residual silver quantity Table 4 (continued) Refill quantity per color negative film Conc. (ratio to complex cyan dye (recoloring property residual silver quantity this

As is apparent from the results of Table 4 above, the recoloring property of cyan dye and the desilvering property greatly deteriorate when the replenishment amount of the bleaching solution is reduced to not more than 300 ml per 1 m² of the color negative film; however, it is seen that the bleaching solution having a concentration of ethylenediaminetetraacetic acid as an example of the organic acids included in the bleaching solution within the scope of the invention shows extremely slight deterioration in both the recoloring property and the desilvering property even when the replenishment amount of the bleaching solution is greatly reduced.

Example 7

Comparative samples were prepared by replacing the magenta coupler (M-203) used for the film sample of Example 6 with the comparative magenta coupler (M'-1) used in Example 1 and the comparative magenta coupler (M'-2) used in Example 3. The film samples of this invention were prepared in a similar manner 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). After storage for three days, treatment was carried out using the bleaching solution. of Example 6, Test No. 69. The cyan dye density and the residual silver content were measured. Also, magenta stains in the unexposed portion were measured. The results are also shown in Table 5. Table 5 Test coupler refill quantity per light-sensitive material acid/complex salt (ratio) cyan dye (recoloring property) residual silver amount magenta spots

As a result, the samples using the existing magenta couplers showed in each case less magenta stain than 0.04 to 0.06 as compared with the magenta coupler outside the present invention.

It was also found that both the recoloring properties of the cyan dye and the residual silver content were good.

Example 8

Tests were conducted following the same procedure as in Example 6, except that the exemplary compounds (I-2), (I-9), (II-28), (II-26), (II-158), (III-33), (III-34), (III-37), (IV-1), (V-71), (V-185), (V-186), (VI-8), (VI-9), (VII-3), (VIII-1), (VIII-4) and (IX-1) were applied to the bleaching solutions used in Example 6, Test No. 69 in the amount described in Table 6, with the bleaching treatment time being 3 minutes. Table 6 Test Bleaching accelerator Residual silver amount Example added amount No addition

As a result, the amount of residual silver was reduced in each case, even though the bleaching treatment time was shortened.

Example 9

Film samples were prepared by the same procedure as in Example 6 except that the exemplary compounds (XI-1), (XI-4), (XI-6) and (XI-11) were used for the green-sensitive silver halide emulsion layer of the film sample prepared by Example 6, and then the same tests as in Example 2 were conducted. The results are shown in Table 7. Table 7 Test Example No. of sensitizing dye Residual silver amount Yellow spots in unexposed section applied

From the result of Table 7, it is understood that in the case where the bleaching solution and the sensitizing dye of the present invention were used in combination, the residual silver amount was further reduced by about one third and the yellow spots in the unexposed portion were reduced.

Example 10

The same tests as in Example 6, Test No. 69 were repeated with the proviso of replacing the color developing agent in the color developing solution used in Example 6, Test No. 69 (Example Compound No. X-2) with the hydrochlorides (D-1) and (D-2) shown below. Furthermore, similar tests were carried out replacing the color developing agent (X-2) with a sulfate of (X-1), 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 at 35% based on the total amount of the bleaching solution, and the treatment was carried out after storage for one week at room temperature. The residual silver amount and magenta spots (bleach spots) of the film samples after the treatment were determined, and the generation of tar in the bleaching solution was monitored. The results are shown in Table 8. Table 8 Test Color developer Residual silver amount Magenta stains Tar properties

In Table 8, 0 means no tar production, means little tar production, and x means the production of tar to such an extent that tar adhered to the film.

It is seen from Table 8 that the use of the color developing agent according to the present invention improves the desilvering property, bleaching stains and the generation of tar.

Example 11

Example 1 was repeated except that the (ethylenediaminetetraacetate) iron (III) complex salt used for the bleaching solution and the bleach-fixing solution in Example 1 was replaced with the iron (III) complex salt of the example compound (XII-4) (1,3-diaminopropanetetraacetate). It was found that the residual silver amount was not generated at all, 0 mg/100 cm², thus the property against the residual silver amount was further improved.

Furthermore, a similar experiment was carried out in which the total amount of the iron salt added was 0.37 mol and the mixing ratio of (ethylenediaminetetraacetate) iron (III) complex salt and iron (III) complex salt of the example compound (XII-4) was 1:1 to 2:1. It was also found that a residual amount of silver was not generated at all.

Claims (11)

1. A process for producing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer which is subjected to image-wise exposure and a subsequent treatment including at least a color development step and a bleaching step, wherein a bleaching solution used in the bleaching step contains at least one iron (III) complex of an organic acid; and wherein the bleaching solution contains at least one organic acid and the bleaching solution is replenished, characterized in that a silver halide color photographic light-sensitive material is treated, wherein at least one layer of the silver halide emulsion layer contains at least one magenta coupler having the general formula (M) wherein Z is a non-metal atom group required to form a nitrogen-containing heterocyclic ring, the ring optionally having a substituent; X is a hydrogen atom or a substituent eliminable by a reaction with an oxidized product of a color developing agent; and R is a hydrogen atom or a substituent; that the organic acid is contained in a range of not more than 10 mol% of the content of the ferric complex of the organic acid contained in the bleaching solution; and that the replenishment amount in the bleaching step is 30 ml to 300 ml per 1 m² of the silver halide color photographic material. 2. Process for producing a light-sensitive colour photographic The silver halide material according to claim 1, wherein the bleaching solution contains at least one of the compounds having the general formulas (I) to (IX) shown below; 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 is 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 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group; A represents or an n₁-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 is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, an alkyl group or ; M is a divalent metal atom; R'' is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including the group condensed with an unsaturated 5- to 6-membered ring) or an amino group; and n1 to n6 and m1 to m5 each represent an integer of 1 to 6; B is an alkylene group having 1 to 6 carbon atoms; Y is -N< or -CH<; R₄ and R₅ each has the same meaning as defined for R₂ and R₃; with the proviso that R₄ and R₅ each represents -B-SZ and that R₂ 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 hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B₁-SZ₁. with the proviso that R₆ and R₇ may be combined to form a ring; Y₁ represents >N- or >CH-; B₁ is an alkylene group having 1 to 6 carbon atoms; Z₁ is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group or ; and n7 is an integer from 1 to 6; general formula (IV): wherein R�8 and R�9 each represent and R₁₀ is an alkyl group or -(CH₂)n8SO⁻ (provided that 1 represents zero when R₁₀ is -(CH₂)n8SO⁻ or represents 1 when it is an alkyl group). G⁻ is an anion; and n8 is 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; with the proviso that Q' has the same meaning as defined for Q₁; general formula (VI): wherein D₁, D₂, D₃ and D₄ each represents a simple bond arm, an alkylene group having 1 to 8 carbon atoms or a vinylene group; and q1, q2, q3 and q4 are each an integer of 0, 1 or 2, wherein the ring formed together with a sulfur atom may be further condensed with a saturated or unsaturated 5- to 6-membered ring, excluding elemental sulfur; general formula VI-13: general formula (VII): where X₂; represents -COOM', -OH, -SO₃M', -CONH₂, -SO₂NH₂, -NH₂, -SH, -CN, -CO₂R₁₆, -SO₂R₁₆, -OR₁₆, -NR₁₆R₁₇, -SR₁₆, -SO₃R₁₆, -NHCOR₁₆, -NHSO₂R₁₆, -OCOR₁₆ or -SO₂R₁₆; Y2; means or a hydrogen atom; and m9 and n9 are each an integer of 1 to 10; R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₇ and R₁₈ are each a hydrogen atom, a lower alkyl group, an acyl group or R₁₆ is a lower alkyl group; R₁₉ represents -NR₂�0 R₂₁, -OR₂₂ or -SR₂₂; R₂�0 and R₂₁ are each a hydrogen atom or a lower alkyl group; and R₂₂ is a group of atoms required to form a ring in combination with R₁₈; R₂�0 or R₁₁ may be combined with R₁₈ to form a ring; M' is a hydrogen atom or a cation, general formula (VIII): wherein Ar is a divalent aryl group or a divalent organic group formed by combining an aryl group with an oxygen atom and/or an alkylene group; B₂ and B₃ are each a lower alkylene group; R₂₃, R₂₄, R₂₅ and R₂₆ each represent a hydroxy-substituted lower alkyl group; and x and y are each 0 or 1; G' is an anion; and z is 0, 1 or 2, general formula (IX): wherein 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 carboxy group. 3. A process for producing a silver halide color photographic light-sensitive material according to claim 1 or 2, wherein at least one layer of the silver halide color photographic light-sensitive material contains a cyan coupler which has the general formula (C): wherein R₂₁ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R₂₄ is an unsubstituted or substituted aryl group; and Z is a hydrogen atom or a group eliminable by a coupling reaction with an oxidizing product of an N-hydroxyalkyl-substituted-p-phenylenediamine derivative as a developing agent. 4. A process for producing a silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein at least one of the substituents in the general formula (M) is an aromatic sulfonyl group represented by the following formula (A) wherein R₁ represents an aliphatic group, an aryl group or a heterocyclic group; m is an integer 1 or 2, wherein R₁ may be the same or different when m is 2; R₂ is 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. 5. A process for producing a silver halide color photographic light-sensitive material according to any one of claims 1 to 4, wherein the organic acid or the organic acid capable of forming the iron (III) complex of the organic acid is a compound represented by the following general formula (XII) or (XIII): wherein E represents a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, -R₈₃OR₈₃OR₈₃- or -R₈₃ZR₈₃-, Z is >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. 6. A process for producing a silver halide color photographic light-sensitive material according to claim 5, wherein the compound represented by formula (XII) or (XIII) is a compound selected from the group consisting of: (XII-1) Ethylenediaminetetraacetic acid (XII-2) Diethylenetriaminepentaacetic acid (XII-4) Propylenediaminetetraacetic acid (XII-5) Triethylenetetraminehexaacetic acid (XII-7) 1,2-Diaminopropanetetraacetic acid (XII-8) 1,3-Diaminopropan-2-ol-tetraacetic acid (XII-19) Ethylenediaminetetraethylenephosphonic acid (XIII-1) Nitrilotriacetic acid (XIII-3) Hydroxyethylimino-di-acetic acid (XIII-5) Nitrilotrimethylenephosphonic acid 7. A process for producing a silver halide color photographic light-sensitive material according to any one of claims 1 to 6, wherein the amount of the bleaching solution to be replenished is 40 ml to 250 ml per 1 m² of the silver halide color photographic light-sensitive material. 8. A process for producing a silver halide color photographic light-sensitive material according to claim 7, wherein the amount of the bleaching solution to be replenished is 50 ml to 200 ml per 1 m² of the silver halide color photographic light-sensitive material. 9. A process for producing a silver halide color photographic light-sensitive material according to claim 2, wherein the bleaching solution contains at least one compound selected from the group consisting of the compounds represented by formula (II), (III), (V) or (VII). 10. A process for producing a silver halide color photographic light-sensitive material according to any one of claims 1 to 9, wherein a color developing solution used for the color developing step contains a color developing agent represented by the following formula (X): wherein R₁₃ is a hydrogen atom, a halogen atom or an alkyl group, the 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, the alkyl or aryl group being optionally substituted; at least one of R₁₄ and R₁₅ is an alkyl group which is 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 with -[-(CH₂)q-O-]p-R₁₆, the alkyl group being optionally further substituted; R₁₆ is a hydrogen atom or an alkyl group having a straight or branched chain with 1 to 5 carbon atoms, and p and q are each an integer from 1 to 5. 11. A process for producing a silver halide color photographic light-sensitive material according to any one of claims 1 to 10, wherein the silver halide photographic light-sensitive material contains at least one of the compounds having the general formula (XI): wherein Z₁₁ and Z₂₁ each represent a group of atoms necessary to form a benzene ring or a naphthalene ring condensed with an oxazole ring; R₄₁ and R₄₂ individually represent an alkyl group, an alkenyl group or an aryl group, R₄₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X₁⁻ is an anion, and n is 1 or 0.