Method for processing a silver halide photosensitive material for color photography

What is claimed is:

1. A method for processing a silver halide color photosensitive material which comprises developing an image-wise exposed color photographic light-sensitive material comprising a support having thereon at least one light-sensitive silver halide emulsion layer containing a silver halide comprising at least 80 mol % silver chloride; at least one emulsion layer thereof comprising a dispersion of a mixture of (i) at least one oil-soluble non-diffusible cyan coupler capable of forming a substantially non-diffusible cyan dye by coupling with the oxidized form of a developing agent, and (ii) a water-insoluble polymer;

in a color developer solution comprising a primary amine color developing agent, and having a chloride ion concentration of from 3.5.times.10.sup.-2 to 1.5.times.10.sup.-1 mol/l, and a bromide ion concentration of from 3.0.times.10.sup.-5 to 1.0.times.10.sup.-3 mol/l.

2. The method as claimed in claim 1, wherein said developer solution comprises from 0.005 to 0.5 mol/l of an organic preservative represented by formulae (I) or (II): ##STR23## wherein R.sup.11 and R.sup.12 each represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group or a substituted or unsubstituted heteroaromatic group, provided that at least one of R.sup.11 and R.sup.12 is a group other than a hydrogen atom, and R.sup.11 and R.sup.12 may be linked to form a saturated or unsaturated 5-membered or 6-membered heterocyclic ring; and ##STR24## wherein R.sup.31, R.sup.32 and R.sup.33 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; R.sup.34 represents a hydroxyl group, a hydroxyamino group, a substituted or unsubstituted akyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group or a substituted or unsubstituted amino group; X.sup.31 represents --CO--, --SO.sub.2 -- or --C(.dbd.NH)--; and n is 0 or 1; provided that when n is 0, R.sup.34 represents an alkyl group, an aryl group or a heterocyclic group; and R.sup.33 and R.sup.34 may be linked to form a heterocyclic ring.

3. The method as claimed in claim 2, wherein R.sup.11 and R.sup.12 each represents a substituted or unsubstituted alkyl group containing 1 to 10 carbon atoms or a substituted or unsubstituted alkenyl group containing 2 to 10 carbon atoms, each said substituted group being substituted with a substituent selected from the group consisting of a hydroxyl group, an alkoxy group, an alkylsulfonyl group, an arylsulfonyl group, an amido group, a carboxyl group, a cyano group, a sulfo group, a nitro group and an amino group.

4. The method as claimed in claim 3, wherein said alkyl group and alkenyl group represented by R.sup.11 and R.sup.12 each contains 1 to 5 Carbon atoms.

5. The method as claimed in claim 2, wherein each of R.sup.31, R.sup.32 and R.sup.33 each represents a hydrogen atom or a substituted or unsubstituted alkyl group containing 1 to 10 carbon atoms; R.sup.34 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted amino group; each said substituted group being substituted with at least one substituent selected from the group consisting of a carboxyl group, a sulfo group, a nitro group, an amino group and a phosphono group; and X.sup.31 represents --CO-- or --SO.sub.2 --.

6. The method as claimed in claim 5, wherein R.sup.31 and R.sup.32 each a represents hydrogen; atom R.sup.34 represents a substituted or unsubstituted alkyl group; and X.sup.31 represents --CO--.

7. The method as claimed in claim 2, wherein said developer solution further comprises at least one compound represented by formulae (III) or (IV): ##STR25## wherein R.sup.71, R.sup.72 and R.sup.73 each represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted heterocyclic group; provided that R.sup.71 and R.sup.72, and R.sup.71 and R.sup.73, or R.sup.72 and R.sup.73 may be linked to form a heterocyclic ring; and ##STR26## wherein X represents a trivalent atom or atomic group necessary for forming a condensed ring; and R.sup.1 and R.sup.2 each represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted aralkylene group.

8. The method as claimed in claim 1, wherein said color developer solution contains not more than 2.0 ml/l of benzyl alcohol.

9. The method as claimed in claim 1, wherein said water-insoluble polymer is organic solvent-soluble, and has a molecular weight of at most 150,000, which is a vinyl polymer or a polyester polymer.

10. The method as claimed in claim 1, wherein said cyan coupler is represented by formula (Va) or (Vb): ##STR27## wherein R.sub.1, R.sub.2 and R.sub.4 each represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group; R.sub.3, R.sub.5 and R.sub.6 each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a substituted or unsubstituted acylamino group; provided that R.sub.3 may be linked with R.sub.2 to form a 5-membered or 6-membered heterocyclic ring; Y.sub.1 and R.sub.2 each represents a hydrogen atom or a coupling-off group; and n is 0 or 1.

11. The method as claimed in claim 10, wherein R.sub.1 represents an aryl group or a heterocyclic group; R.sub.2 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; R.sub.3 represents a hydrogen atom; R.sub.4 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; R.sub.5 represents an alkyl group containing 1 to 15 carbon atoms or a substituted methyl group substituted with a substituent selected from the group consisting of an arylthio group, an alkylthio group, an acylamino group, an aryloxy group and an alkyloxy group; R.sub.6 represents a hydrogen atom or a halogen atom; and Y.sub.1 and Y.sub.2 each represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamido group.

12. The method as claimed in claim 11, wherein R.sub.1 represents an aryl group substituted with a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a sulfamido group, an oxycarbonyl group, and a cyano group; R.sub.2 represents a substituted aryloxy-substituted alkyl group; R.sub.4 represents a substituted aryloxy-substituted alkyl group; R.sub.5 represents an alkyl group containing 2 to 4 carbon atoms; R.sub.6 represents chlorine or fluorine; Y.sub.2 represents chlorine or fluorine; and when n is 0, Y.sub.1 represents chlorine or fluorine.

13. The method as claimed in claim 1, wherein said silver halide in said light-sensitive silver halide emulsion layer contains at least 95 mol % silver chloride.

14. The method as claimed in claim 13, wherein said silver halide contains at least 98 mol % silver chloride.

15. The method as claimed in claim 14, wherein said light-sensitive silver halide emulsion layer contains at most 0.8 g/m.sup.2 of silver contained in said silver halide.

16. The method as claimed in claim 1, wherein said color developer has a chloride ion concentration of 4.times.10.sup.-2 to 1.times.10.sup.-1 mol/l.

17. The method as claimed in claim 1, wherein said color developer has a bromide ion concentration of from 5.0 .times.10.sup.-5 to 5.times.10.sup.-4 mol/l.

18. The method as claimed in claim 1, wherein said dispersion additionally comprises an auxiliary solvent and the weight ratio of said polymer to said auxiliary solvent is about 1:1 to about 1:50.

19. The method as claimed in claim 1, wherein the weight ratio of said polymer to said cyan coupler is from 1:20 to 20:1.

20. The method as claimed in claim 9, wherein said vinyl polymer or polyester polymer has a bonding group of the formula ##STR28##

21. The method as claimed in claim 9, wherein said vinyl polymer or polyester is a methacrylate polymer, an acrylamide polymer, or a methacrylamide polymer.

22. The method as claimed in claim 20, wherein said vinyl polymer or polyester is an acrylamide polymer or a methacrylamide polymer.

23. The method as claimed in claim 13, wherein said light-sensitive silver halide emulsion layer contains silver in an amount of 0.3 to 0.75 g/m.sup.2.

24. The method as claimed in claim 8, wherein said color developer solution contains no benzyl alcohol.

25. The method as claimed in claim 1, wherein said color developer solution contains substantially no sulfite ion.

Description Submit all comments and votes

FIELD OF THE INVENTION

The present invention relates to a method for processing a silver halide photosensitive material for color photography and more particularly to a method for rapid development of a high-silver-chloride (high-chloride) silver halide photosensitive material.

BACKGROUND OF THE INVENTION

In the photographic processing of photosensitive materials for color photography, the recent demand for quick print delivery and reduced commercial laboratory work load has made it necessary to reduce the photographic processing time. While the commonest approach to a shortening of processing time is to increase the processing temperature and/or the replenishment rate, many other procedures such as intensified agitation and addition of accelerators have been proposed.

Particularly, for rapid color development and/or reducing the replenishment rate, the use of a color photosensitive material employing a silver chloride emulsion instead of conventional silver bromide and silver iodide emulsions has been proposed. For example, PCT WO-04534/1987 discloses a rapid processing technique in which a chloride-rich silver halide color photosensitive material is treated with a color developer which is substantially free from sulfite ions and benzyl alcohol.

However, the above-mentioned method is disadvantageous, since when it is used in an automatic developing apparatus for paper, fog streaks readily appear. These are presumably in-liquid pressure sensitization due to pressure applied to the silver halide emulsion by contact of a photosensitive material with a roller or the like in the developing tank of the automatic developing apparatus.

Furthermore, in continuous processing, this method allows remarkable variations in photographic characteristics (in particular minimum density) and marked staining of the white background.

The rapid processing of a high-silver-chloride photosensitive material for color photography presents problems such as in-liquid pressure sensitization fogging and variation of photographic characteristics, and is unsuitable for practical use.

JP-A-58-95345 and 59-232342 (the term "JP-A" herein used means an unexamined published Japanese patent application) describe the use of organic antifogging agents for the purpose of minimizing the variations in photographic characteristics (in particular, fogging) in rapid processing using a high-silver-chloride photosensitive material for color photography. However, their antifogging effect is unsatisfactory and, in general, they fail to prevent the above-mentioned sensitization streaks due to pressure in the liquid phase or an increase in minimum density during continuous processing. Furthermore, their effect decreases with the progress of continuous processing.

JP-A-61-70552 describes a method for reducing the rate of developer replenishment by using a high-chloride silver halide photosensitive material for color photography and adding the replenisher to the developing bath during development at a rate such that no overflowing may occur. JP-A-63-106655 discloses a method of processing a silver halide photosensitive material for color photography whose silver halide emulsion layer has a high silver chloride content, with a color developer containing a hydroxylamine compound and a chloride at a minimum concentration for the purpose of process stabilization.

JP-A-63-106655 describes a method of processing a photosensitive material having a silver chloride proportion of 70 mole percent or more with a developer containing a chloride in a concentration of at least 2.times.10.sup.-2 moles.

However, these methods also are unsuited for practical use, since they pressure sensitization streaks are formed upon processing in an automatic developing apparatus or the photographic characteristics vary during continuous processing.

SUMMARY OF THE INVENTION

Accordingly, it is a first object of the invention to provide a method of rapid processing of a high-silver-chloride photosensitive material for color photography without various types of pressure sensitization fogging.

It is a second object of the invention to provide a method of processing a high-silver-chloride photosensitive material for color photography which provides a high maximum density and a low minimum density as well as markedly reduced variations in photographic characteristics (in particular, minimum density).

It has now been found that these and other objects of the present invention are attained by a method for processing a silver halide color photosensitive material which comprises developing a color photographic light-sensitive material comprising a support having thereon at least one light-sensitive silver halide emulsion layer containing a silver halide comprising at least 80 mol % silver chloride; at least one emulsion layer thereof comprising a dispersion of a mixture of (i) at least one oil-soluble non-diffusible cyan coupler capable of forming a substantially non-diffusible cyan dye by coupling with the oxidized form of a developing agent, and (ii) a water-insoluble polymer;

in a color developer solution comprising a primary amine color developing agent, and having a chloride ion concentration of from 3.5.times.10.sup.-2 to 1.5.times.10.sup.-1 mol/l, and a bromide ion concentration of from 3.0.times.10.sup.-5 to 1.0.times.10.sup.-3 mol/l.

DETAILED DESCRIPTION OF THE INVENTION

Although the chloride ion is well known as an antifogging agent, its effect is limited. Even when used in large amounts, it cannot completely prevent increasing fogging in a continuous processing apparatus or the formation of fog streaks in processing in an automatic developing apparatus, but may produce adverse effects, by retarding the development and/or reducing the maximum density.

The bromide ion is also known as an antifogging agent. However, when used alone, it suppresses the development process and reduces the maximum density and sensitivity, and therefore is not suited for practical use although when used in adequate amounts, it can prevent fogging in continuous processing as well as pressure fogging streaks.

As a result of intensive investigations, the present inventors have found that the formation of pressure fogging streaks during processing in an automatic developing apparatus and the variations in photographic characteristics (especially, minimum density) in continuous processing can be prevented without any substantial decrease in maximum density when a photosensitive material in which the silver chloride content is not less than 80 mole percent and which contains at least one cyan coupler dispersed by means of a hydrophobic polymer is treated with a color developer containing 3.5.times.10.sup.-2 to 1.5.times.10.sup.-1 moles/liter of chloride ion and 3.0.times.10.sup.-5 to 1.0.times.10.sup.-3 mole/liter of bromide ion.

When the chloride ion and bromide ion are used alone, such effects are never produced, and it is unexpected and surprising that such effects are obtained when they are used in combination, in accordance with the invention in the respective concentration ranges specified above.

The detailed mechanisms resulting in these surprising benefits remain unknown, but without being limited in any way by theory, are considered to be as follows.

The pressure fogging streaks appearing upon processing on an automatic developing apparatus are presumably due to excessive pressure applied to the exposed photosensitive material in the color developer and formation of fog nuclei or centers as a result of intensification in the pressurized portions. It is considered that the physical strength of the coating layer is improved by dispersing cyan couplers with the polymer specified above, so that the external force applied to the coat layer can be dispersed efficiently and, consequently, the fog center formation can be inhibited.

It is further considered that the bromide and chloride ions contained in the developer in adequate amounts in accordance with the invention selectively prevent the fog centers from being developed and thereby inhibit fogging without retarding the development or reducing the maximum density or sensitivity. Such a selective development-inhibiting effect resulting from the combination of the bromide and chloride ions in the respective specific concentration ranges cannot be fully explained in terms of a change in reduction potential of silver ion in the presence of halogens alone. It is considered likely that the state of adsorption of bromide and chloride ions on silver halide grains is of great influence.

The effect of inhibiting variations in photographic characteristics in continuous processing cannot be exclusively due to high developing activity resulting from the use of a high-chloride silver emulsion and to balanced activity reduction due to the presence of the bromide and chloride ions in adequate amounts, i.e., to high activity-high restraint type development.

In accordance with the invention, the silver halide emulsion is substantially composed of silver chloride. The term "substantially" as used herein means that the silver chloride content is not less than 80 mole percent, preferably not less than 95 mole percent, more preferably not less than 98 mole percent, based on the whole silver halide content. For rapid processing, a higher silver chloride content is preferred.

In accordance with the invention, the color developer contains 3.5.times.10.sup.-2 to 1.5.times.10.sup.-1 moles/liter, preferably 4.times.10.sup.-2 to 1.times.10.sup.-1 mole/liter, of chloride ions. Chloride ion concentrations exceeding 1.5.times.10.sup.-1 moles/liter are disadvantageous in that the development is retarded, preventing rapid development and high maximum density. At chloride ion concentrations below 3.5.times.10.sup.-2 moles/liter, the formation of pressure fogging streaks cannot be prevented and the variations in photographic characteristics (especially, minimum density) in continuous processing are great.

In accordance with the invention, the color developer contain 3.0.times.10.sup.-5 to 1.0.times.10.sup.-3 mole/liter, preferably 5.0.times.10.sup.-5 to 5.times.10.sup.-4 moles/liter, of bromide ion. Bromide ion concentrations exceeding 1.times.10.sup.-3 mole/liter retard the development and reduce the maximum density and sensitivity. At levels below 3.0.times.10.sup.-5 moles/liter, the formation of pressure fogging streaks cannot be inhibited and variations in photographic characteristics (in particular, minimum density) occur in continuous processing.

The chloride ion and bromide ion may be added directly to the developer or may be released from the photosensitive material in the developer.

The chloride ion source for direct addition to the color developer, includes sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Preferred among them are sodium chloride and potassium chloride.

Either ion may further be supplied from a fluorescent or optical brightener added to the developer. The bromide ion source include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, and thallium bromide. Among these, potassium bromide and sodium bromide are preferred.

Where they are released from the photosensitive material in the developer into the developer solution, the chloride ion and bromide ion both may be supplied from the emulsion layer or some other layer.

In the present invention, the color developer is preferably substantially free from sulfite ions from the viewpoints of stabilized continuous processing and streaky pressure fog prevention. For inhibiting or preventing developer degradation, it is also possible to refrain from using the developer for a prolonged period of time; to use a physical means, such as a floating lid or a reduced bath opening ratio, for minimizing the influence of air oxidation; or to use a chemical means, for example, to lower the developer temperature or add an organic preservative. For simplicity, the use of an organic preservative is advantageous.

The term "organic preservative" as used herein means any and all organic compounds which, when added to a processing solution for color photographic light-sensitive materials, would reduce the rate of degradation of the aromatic primary amine color developing agent. Thus, an organic preservative is an organic compound which inhibits atmospheric or other oxidation of color developing agents. Particularly useful organic preservatives are hydroxylamine derivatives (exclusive of hydroxylamine, here and below), hydroxamic acid compounds, hydrazines, hydrazides, phenols, .alpha.-hydroxyketones, .alpha.-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed cyclic amines. These compounds are disclosed in JP-A-63-4235, JP-A-63-30845, JP-A-6321647, JP-A-63-44655, JP-A-63-53551, JP-A-63-43140, JP-A-63-56654, JP-A-63-58346, JP-A-63-43138, JP-A-63-146041, JP-A-63-170642, JP-A-63-44657 and JP-A-63-44656, U.S. Pat. Nos. 3,613,503 and 2,494,903, JP-A-52-143020, JP-B-48-30496 (the term JP-B having used means an "unexamined Japanese patent publication") and so on.

The following preferred organic preservatives are illustrated by structural formulas and specific examples, but the present invention is not to be construed as being limited thereto.

The compounds described below are added to color developers in an amount of 0.005 mole/liter to 0.5 mole/liter, preferably 0.03 mole/liter to 0.1 mole/liter.

In particular, the addition of hydroxylamine derivatives and/or hydrazine derivatives is preferred.

Preferred hydroxylamine derivatives are compounds of formula (I): ##STR1## wherein R.sup.11 and R.sup.12, which may be the same or different, each represents hydrogen, an unsubstituted or substituted C.sub.1-10, preferably C.sub.1-5 alkyl group, an unsubstituted or substituted C.sub.2-10 alkenyl group, an unsubstituted or substituted C.sub.6-10 aryl group or a substituted or unsubstituted heteroaromatic group, provided that when R.sup.11 is hydrogen, R.sup.12 is a group other than hydrogen; R.sup.11 and R.sup.12 may be linked to form, together with the nitrogen atom, a saturated or unsaturated five- or six-membered heterocycle containing a carbon, hydrogen atom, a halogen atom, oxygen, nitrogen, or sulfur.

It is preferred that R.sup.11 and R.sup.12 each represents an alkyl or alkenyl group. The number of carbon atoms in each group is preferably up to 10, in particular up to 5. The nitrogen-containing heterocycle formed by R.sup.11 and R.sup.12 together with the adjacent nitrogen atom includes piperidyl, pyrrolidyl, N-alkylpiperazinyl, morpholyl, indolinyl and benzotriazole.

Preferred substituents for R.sup.11 and R.sup.12 include hydroxyl, alkoxy, alkylsulfonyl, arylsulfonyl, amido, carboxyl, cyano, sulfo, nitro and amino groups. Specific examples of compounds represented by formula (I) are as follows, but the present invention is not to be construed as being limited thereto. ##STR2##

The following are preferred hydrazine and hydrazide organic preservatives: ##STR3## wherein R.sup.31, R.sup.32 and R.sup.33, which may be the same or different, each represents hydrogen or a substituted or unsubstituted C.sub.1-10 alkyl, C.sub.6-10 aryl or heterocyclic group; R.sup.34 represents a hydroxyl group, a hydroxy-amino group or a substituted or unsubstituted C.sub.1-10 alkyl, C.sub.6-10 aryl, C.sub.1-10 heterocyclic, C.sub.1-10 alkoxy, C.sub.6-10 aryloxy, carbamoyl or amino group. The heterocyclic group is a five- or six-membered, saturated or unsaturated group and may contain C, H, 0, N, S and halogen atoms. X.sup.31 is a divalent linking group selected from --CO--, --SO.sub.2 -- and --C(.dbd.NH)--, and n is 0 or 1. In particular, when n is 0, R.sup.34 is an alkyl, aryl or heterocyclic group; and R.sup.33 and R.sup.34 may be linked to form a heterocycle together with the adjacent nitrogen atom.

Those compounds represented by formula (II), in which R.sup.31, R.sup.32 and R.sup.33 each is hydrogen or a C.sub.1 -C.sub.5 alkyl group are preferred. Particularly preferred are those in which R.sup.31 and R.sup.32 each is hydrogen.

Preferred as the group R.sup.34 in formula (II) are alkyl, aryl, alkoxy, carbamoyl and amino groups. An alkyl or substituted alkyl group is particularly preferred. The subsituted alkyl group that is preferred be substituted with at least one carboxyl, sulfo, nitro, amino, or phosphono group. X.sup.31 is preferably --CO--, or --SO.sub.2 --, and more preferably --CO--.

Specific compounds represented by formula (II) are described below, but the present invention is not to be construed as being limited thereto: ##STR4##

The combined use of a compound of the above formula (I) or (II) and an amine of formula (III) or (IV) given below is preferred to improve color developer stability and continuous processing process stability. Formula (III): ##STR5## In the above formula, R.sup.71, R.sup.72 and R.sup.73, which may be the same or different each is hydrogen or an alkyl, alkenyl, aryl, aralkyl or heterocyclic group having 1 to 10 carbon atoms. R.sup.71 and R.sup.72, R.sup.71 and R.sup.73, or R.sup.72 and R.sup.73 may be linked to form, together with the adjacent nitrogen atom, a nitrogen-containing heterocyclic group.

The groups R.sup.71, R.sup.72 and R.sup.73 may optionally be substituted. Hydrogen or an alkyl group is particularly preferred as each of R.sup.71, R.sup.72 and R.sup.73. The substituents include hydroxyl, sulfo, carboxyl, halogen, nitro, and amino groups. Specific examples of compounds of formula (III) are as follows, but the present invention is not to be construed as being limited thereto: ##STR6## Formula (IV): ##STR7## In the above formula, X is a trivalent atom or atomic group required for completing the condensed ring system and R.sup.1 and R.sup.2 each is an alkylene, arylene, alkenylene or aralkylene group.

The groups R.sup.1 and R.sup.2 may be the same or different.

Particularly preferred compounds of formula (IV) are those represented by formula (IV) are those represented by formula (IV-a) or (IV-b): ##STR8##

In the above formula, X.sup.1 is ##STR9## R.sup.1 and R.sup.2 are as defined in Formula (IV) and R.sup.3 is has the same definition as R.sup.1 or R.sup.2, or is --CH.sub.2 CO--.

In formula (IV-a), X.sup.1 is preferably ##STR10## and R.sup.1, R.sup.2 and R.sup.3 each preferably contains not more than 6 carbon atoms, more preferably not more than 3 carbon atoms and most preferably 2 carbon atoms.

R.sup.1, R.sup.2 and R.sup.3 each preferably is an alkylene or arylene group and more preferably an alkylene group. ##STR11## In the above formula, R.sup.1 and R.sup.2 each is defined in formula (IV).

In formula (IV-b), R.sup.1 and R.sup.2 each preferably contains not more than 6 carbon atoms. R.sup.1 and R.sup.2 each preferably is an alkylene or arylene group and more preferably an alkylene group.

Among the compounds of general formula (IV-a) and (IV-b), those of general formula (IV-a) are particularly preferred.

Specific examples of compounds represented by formula (IV) are as follows, but the present invention is not to be construed as being limited thereto. ##STR12##

The combined use of at least one of the above-mentioned organic preservatives of general formula (I) or (III) and at least one of the preservatives of general formula (III) or (IV) is preferred.

The above-described organic preservatives are either commercially available on the market or synthesizable by the methods described in Japanese Patent Application No. 124038/1987 and No. 24374/1987, for instance.

The color developer used in accordance with the present invention contains a conventional aromatic primary amine color developing agent. p-Phenylenediamines are preferred and the following specific examples are suitable, but the present invention is not to be construed as being limited thereto:

D-1: N,N-Diethyl-p-phenylenediamine

D-2: 4-[N-Ethyl-N-(.beta.-hydroxyethyl)amino]aniline

D-3: 2-Methyl-4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]-aniline

D-4: 4-Amino-3-methyl-N-ethyl-N-(.beta.-methanesulfonamidoethyl)aniline

These p-phenylenediamine derivatives may be used as the corresponding sulfates, hydrochlorides, p-toluenesulfonates and other salts. The amount of aromatic primary amine developing agent is preferably about 0.1 to 20 g and more preferably about 0.5 to 10 g per liter of the developer.

The pH of the color developer to be used in accordance with the present invention is preferably 9 to 12 and more preferably 9 to 11.0, and this color developer may further contain other known developing agents.

The above-mentioned pH is preferably established with buffers. Among the buffers useful for this purpose are sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the above buffer or buffers added to the color developer is preferably not less than 0.1 mole/l and more preferably in the range of 0.1 to 0.4 mole/l.

In addition, the color developer may contain various chelating compounds for preventing precipitation of calcium and magnesium or improving the stability of the solution. The following specific examples are not to be construed as limiting the present invention.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehxaacetic acid, N,N,N-trimethylenesulfonic acid, ethylenediamine-N,N,N',N'-tetramethylenesulfonic acid, 1,3-diamino-2-propanoltetraacetic acid, trans-cyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine-o-hydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, N,N'-bis(2 hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, catechol 3,4,6-trisulfonic acid, catechol-3,5disulfonic acid, 5-sulfosalicyclic acid, and 4-sulfosalicyclic acid.

These chelating agents may be used in combination as necessary.

The amount of chelating agent or agents should only be sufficient to block the metallic ions in the color developer. For example, it is about 0.1 to 10 g per liter.

If necessary, an optional development accelerator can be incorporated in the color developer.

Examples of the development accelerator include the thioether compounds described in JP-B-47-16088, 47-5987, 38-7826, 45-12380, 45-9019 and U.S. Pat. No. 3,813,247; the p-phenylenediamine compounds described in JP-A-52-49829 and 50-15554; the quaternary ammonium salts described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and No. 52-43429; the p-aminophenol compounds described in U.S. Pat. Nos. 2,610,122 and 4,119,462; the amine compounds described in U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346; the polyalkylene oxides described in JP-B-37-16088 and 42-25201, U.S. Pat. No. 3,128,183, JP-B-40-11431 and No. 42-23883 and U.S. Pat. No. 3,532,501; 1-phenyl-3-pyrazolidone compound, hydrazines, mesoionic compounds, ionic compound, and imidazoles.

The color developer is preferably substantially free of benzyl alcohol. The term "substantially free" means that the benzyl alcohol content is not more than 2.0 ml per liter of color developer or, more preferably, nil. When substantially free of benzyl alcohol, the color developer is advantageous in continuous processing, with minimum variations in photographic characteristics.

In the present invention, an appropriate antifogging can be used, as necessary, in addition to chloride and bromide ions. As the antifoggant, alkali metal halides such as potassium iodide and various organic antifoggants can be employed. Representative organic antifoggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-triazolybenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer to be used in the present invention preferably contains fluorescent brightener. The preferred examples of fluorescent brightener are 4,4'-diamino-2,2'-disulfostilbene compounds. The amount of the brightener added ranges from 0 to 10 g and preferably from 1 to 6 g/1.

If necessary, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added to the developer solution.

The processing temperature with the color developer according to the present invention is 20.degree. to 50.degree. C. and preferably 30.degree. to 40.degree. C. The developing time is 20 seconds to 5 minutes and preferably 30 seconds to 2 minutes.

In the present invention, the step of color development is followed by treatment for removal of silver salts. The silver removal treatment generally includes a bleaching step and a fixation step. It is particularly preferable, however, that the bleaching and fixation are performed simultaneously.

The bleach or bleach-fix bath used in the invention may contain a rehalogenating agent such as a bromide (e.g., potassium bromide, sodium bromide, ammonium bromide), a chloride (e.g., potassium chloride,sodium chloride, ammonium chloride) or an iodide (e.g., ammonium iodide). If necessary, this bath may further contain at least one buffer (for maintaining pH at a constant level), for example an inorganic or organic acid and an alkali metal or ammonium salt thereof, such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, or tartaric acid, and/or a corrosion inhibitor, such as ammonium nitrate or guanidine.

The fixing agent used in the bleach-fix bath or fix bath in the invention may be any of known fixing agents, i.e., water soluble silver halide dissolving agents, such as thiosulfates (e.g., sodium thiosulfate, ammonium thiosulfate), thiocyanates (e.g., sodium thiocyanate, ammonium thiocyanate), thioether compounds (e.g., ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol) and thioureas. These may be used either alone or in combination. The particular bleach-fix bath described in JP-A-55-155354 containing a large quantity of a halide, such as potassium iodide, in combination with a fixing agent may also be used. In the practice of the invention, the use of a thiosulfate, in particular ammonium thiosulfate, is preferred. The fixing agent is used preferably in an amount of 0.3 to 2 moles, more preferably within the range of 0.5 to 1.0 mole, per liter of bath.

In the practice of the invention, the bleach-fix bath or fix bath preferably has a pH within the range of 3 to 10, more preferably within the range of 5 to 9. At lower pH levels, the silver removal is promoted but the degradation of the bath and the conversion of cyan dyes to their leuco forms are accelerated. Conversely, at higher pH levels, the silver removal is retarded and staining tends to occur with ease.

For pH adjustment, there may be added hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonates, ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, or potassium carbonate as necessary.

The bleach-fix bath may further contain a fluorescent brightener, or optical brightener, an antifoaming agent, a surfactant, polyvinylpyrrolidone and/or an organic solvent such as methanol.

In the practice of the invention, the bleach-fix bath or fix bath contains, as a preservative, a sulfite ion-releasing compound, such as a sulfite (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), a bisulfite (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite) or a metabisulfite (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). This compound is used preferably in a concentration of about 0.02 to 0.50 mole/liter, more preferably 0.04 to 0.40 mole/liter calculated in terms of the sulfite ion.

While sulfites are generally used as preservatives, ascorbic acid, carbonyl-bisulfite adducts, sulfinic acids, or carbonyl compounds may also be added.

Furthermore, a buffer, a fluorescent brightener, a chelating agent, an antifungal agent and so on may be added to the bath.

The silver halide photosensitive material for color photography according to the invention is generally subjected to a processing sequence of desilvering (fixation, bleach-fix) and washing