EP0298321B1

EP0298321B1 - Silver halide color photographic material

Info

Publication number: EP0298321B1
Application number: EP19880110100
Authority: EP
Inventors: Masakazu Fuji Photo Film Co. Ltd. Morigaki; Nobuo Fuji Photo Film Co. Ltd. Seto
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1987-06-25
Filing date: 1988-06-24
Publication date: 1995-05-10
Anticipated expiration: 2008-06-24
Also published as: DE3853742D1; JPH07122745B2; EP0298321A3; EP0298321A2; JPS642042A; DE3853742T2

Description

The present invention relates to a silver halide color photographic light-sensitive material which exhibits excellent fastness to light, heat and humidity and exhibits less formation of stain.
When a silver halide color photographic material is imagewise exposed and developed with an aromatic amine color developing agent, dye images are formed by a reaction of dye image forming coupler(s) (hereinafter simply referred to as coupler(s)) and an oxidation product of the color developing agent formed as the result of development. For a multicolor photographic material, a combination of a yellow coupler, a cyan coupler, and a magenta coupler is usually used.
In general, the quality of photographic images obtained from silver halide color photographic materials is not permanent and degrades during preservation with the lapse of time. Particularly, with respect to color photographs, when they are exposed to light for a long period of time or preserved under conditions of high temperature and high humidity, color fading or discoloration of dye images and discoloration of the white background ordinarily occur and the color images degrade. This degradation of the color image is a fatal defect for recording materials.
In order to eliminate such a defect, various proposals have hitherto been made. Among these proposals, methods of using color fading preventing agents are extremely effective. As such color fading preventing agents, there are known, for example, hydroquinones, hindered phenols, tocopherols, chromans, coumarans, and the compounds formed by etherifying the phenolic hydroxy groups of these compounds as described in U.S. Patents 3,935,016, 3,930,866, 3,700,455, 3,764,337, 3,432,300, 3,573,050 and 4,254,216, British Patents 2,066,975 and 1,326,889, Japanese Patent Publication No. 30462/76.
These compounds may have the effect of preventing color fading and discoloration of dye images, but since the effect is yet insufficient for meeting the customers' requirement for high image quality and the use of these compounds changes the hue, forms fogs, causes poor dispersibility, and causes fine crystals after coating silver halide emulsions, overall excellent effects for color photography have not yet been obtained by the use of these compounds.
Further, it has recently been found that color stain occurs during preservation after development processing owing to the fact that components of the processing solutions remain in the processed photographic materials. Of the components of processing solutions, the use of a color developing agent is particularly of concern because it causes the occurrence of color stain. For the purpose of preventing the occurrence of color stain, the effectiveness of certain amine compounds has been proposed in U.S. Patents 4,463,085 and 4,483,918, Japanese Patent Application (OPI) Nos. 218445/84 and 229557/84, (the term "OPI" as used herein means a "published unexamined patent application").
However, these compounds are still insufficient in achieving an overall preservability of color photographs, although some degree of improvement in preventing the occurrence of color stain has been observed.
As described above, in the case of using color photographs as recording materials to be preserved for a long period of time, their preservability is not sufficient and thus, further improvement in preservability has been desired.
EP-0-0255722 and EP-A-0258662 which are comprised in the state of the art according to Art. 54(3) EPC disclose a silver halide color photographic material comprising a compound satisfying the following formula (I), (II) or (III) and a color fading agent.
It is the object of the present invention to provide a color photographic light-sensitive material with which fastness of color images formed is extraordinarily improved, the occurrence of yellow stain of the white background in uncolor-formed portions due to light, heat and humidity is exceptionally prevented, the occurrence of color stain caused by the components of processing solutions carried into the color photographic material after development processing, particularly due to a color developing agent remaining therein, is extremely prevented and which exhibits remarkable improvement in preservability.
Said object is accomplished by a silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer, wherein the silver halide color photographic material contains

(1) at least one compound represented by the general formula (I) or (II) and at least one compound represented by the general formula (III), each compound of the formula (I), (II), and (III) including dimers or higher polymers containing at least one moiety derived from the compounds:

wherein R₁ and R₂ each represents an aliphatic group, an aromatic group or a heterocyclic group; X represents a group capable of being released upon a reaction of A with an aromatic amine developing agent; A represents a group capable of reacting with an aromatic amine developing agent to form a chemical bond; n represents 0 or 1; if n is 0, X represents a halogen atom; B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or an aliphatic or aromatic sulfonyl group; Y represents a group capable of accelerating the addition of an aromatic amine developing agent to the compound represented by the general formula (II); wherein R₁ and X, or Y and R₂ or B may be connected to each other to form a cyclic structure; M represents an atom or an atomic group forming an inorganic salt or an organic salt,

wherein R₁₅ and R₁₆, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, wherein R₁₅ and R₁₆ may be connected to each other to form a 5-membered to 7-membered ring; R₁₇, R₁₈, R₂₀and R₂₁ which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aliphatic or aromatic sulfonyl group, a ureido group, or a urethane group, provided that at least one of R₁₇ and R₁₈ and at least one of R₂₀ and R₂₁ each represents a hydrogen atom; R₁₉ and R₂₂ each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group; R₁₉ may further represent an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; wherein at least two of R₁₇, R₁₈ and R₁₉ may be connected to each other to form a 5-membered to 7-membered ring, and at least two of R₂₀, R₂₁ and R₂₂ may be connected to each other to form a 5-membered to 7-membered ring; R₂₃ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R₂₄ represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, an acyloxy group or an aliphatic or aromatic sulfonyl group; R₂₅ represents a hydrogen atom or an alkali-hydrolizable group; and R_io, R_11' R₁₂, R₁₃, and R₁₄, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, -SR₂₆, -OR₂₆,
(wherein R₂₆ and R₂₇, which may be the same or different in the case of -NR₂₆R₂₇, each represents a hydrogen atom, an aliphatic group, an alkoxy group, or an aromatic group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic sulfonamido group, a sulfamoyl group, a ureido group, a urethane group, a carbamoyl group, a sulfo group, a carboxy group, a nitro group, a cyano group, an alkoxyoxalyl group, an aryloxyoxalyl group, an aliphatic or aromatic sulfonyloxy group,
- -P(R₂₆)₃,
  -P (OR₂₆)₃, (wherein R₂₆ has the same meaning as defined above), or a formyl group; and
(2) at least one compound selected from the group consisting of organic color fading preventing agents represented by the general formula (IV) and dimers or higher polymers containing at least one moiety derived from the agents, organic metal complexes containing copper, cobalt, nickel, palladium or platinum as the central metal and having at least one organic ligand having at least one atom which coordinates with the central atom and dimers or higher polymers containing at least one moiety derived from the complexes:
wherein R₃₀ represents an aliphatic group, an aromatic group or a heterocyclic group; R₃₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or
R₃₂, R₃₃ and R₃₄, which may be the same or different, each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group or an aryloxy group; W represents -0-, -S- or
R₃₅ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy-radical group or a hydroxy group; wherein R₃₀ and R₃₁ or R₃₅ and R₃₀ or R₃₁ may be connected to each other to form a 5-membered to 7-membered ring.

The above described object is also accomplished by a method for producing color images which comprises imagewise exposing a silver halide color photographic material containing at least one dye image forming coupler and subjecting the photographic material exposed to a color photographic processing in the presence of the above compounds of (1) and (2).
The present invention also provides a color photographic print comprising a reflective support having thereon at least one of a layer containing a yellow image-forming dye, a layer containing a magenta image-forming dye and a layer containing again image-forming dye, said photographic print having at least one layer containing the above compounds of (1) and (2).
The compounds of (1) and (2) may be incoporated in at least one hydrophilic colloidal layer in the photographic material. It is preferred that the compounds are incorporated in a silver halide emulsion layer, and it is more preferred that the compounds are incorporated in a silver halide emulsion layer containing a magenta coupler.
Of the compounds represented by the general formula (I) or (II), those having a second-order reaction rate constant K₂ (80°C) in a reaction with p-anisidine measured by a method as described in EP-A-0,258,662 in a range from 1.0 f/mol·s to 1×10^-5 f/mol·s are preferred in order to better achieve the effect of the present invention.
By using the compounds of (1) and (2) the occurrence of color stain caused by the components of processing solutions remaining in the photographic material after development processing can be markedly prevented, and prevention from degradation of color image and occurrence of yellow stain of the white background during preservation for a long period of time can be achieved. In particular, the degree of prevention from degradation of color image and occurrence of yellow stain of the white background is extremely high and such effects can not be expected from combinations of hitherto known color fading preventing agents.
At least one compound selected from compounds represented by the general formula (I) or (II) and at least one compound represented by the general formula (III) are employed together.
Now, the compounds represented by the general formula (I), (II) or (III) are described in more detail below.
The term "aliphatic group" as used in the present invention represents a straight chain, branched chain or cyclic alkyl, alkenyl or alkynyl group and these groups may be substituted with a substituent. The term "aromatic group" as used in the present invention may be a carbocyclic series aromatic group (examples for R_1' R₂, B or R include a phenyl group, a naphthyl group), or a heterocyclic series aromatic group (examples for R_1' R₂, B or R include a furyl group, a thienyl group, a pyrazolyl group, a pyridyl group, an indolyl group) and the group may be a monocyclic series or condensed ring series (e.g., a benzofuryl group, a phenanthridinyl group). Furthermore, these aromatic rings may have a substituent.
The term "heterocyclic group" used in the present invention represents a group having a 3-membered to 10-membered ring having carbon atom(s), oxygen atom(s), nitrogen atom(s), or sulfur atom(s) as nucleus- forming atoms, the heterocyclic ring itself may be a saturated ring or an unsaturated ring (examples for R_1' R₂, B or R include a chromanyl group, a pyrrolidyl group, a pyrrolinyl group, a morpholinyl group), and further the ring may be substituted with a substituent.
X in the general formula (I) represents a group capable of being released upon a reaction of A with an aromatic amine developing agent and preferably represents a group connected to A through an oxygen atom, a sulfur atom or a nitrogen atom (e.g., a 3-pyrazolyloxy group, a 3H-1,2,4-oxadiazolin-5-oxy group, an aryloxy group, an alkoxy group, an alkylthio group, an arylthio group, a substituted N-oxy group) or a halogen atom.
A in the general formula (I) represents a group capable of reacting with an aromatic amine developing agent to form a chemical bond. Such groups includes a group containing an atom of low electron density, for example,
When X is a halogen atom, n represents 0. In the above described formulae, L represents a single bond, an alkylene group, -O-, -S-,
(e.g., a carbonyl group, a sulfonyl group, a sulfinyl group, an oxycarbonyl group, a phosphonyl group, a thiocarbonyl group, an aminocarbonyl group, a silyloxy group).
Y has the same meaning as Y defined in the general formula (II), and Y' has the same meaning as defined for Y Y and Y' may be the same or different.
R' and R", which may be the same or different, each represents -L"'-R_o. R_o has the same meaning as defined for R₁.
R'" represents a hydrogen atom, an aliphatic group (e.g., a methyl group, an isobutyl group, a tert-butyl group, a vinyl group, a benzyl group, an octadecyl group, a cyclohexyl group), an aromatic group (e.g., a phenyl group, a pyridyl group, a naphthyl group), a heterocyclic group (e.g., a piperidinyl group, a pyranyl group, a furyl group, a chromanyl group), an acyl group (e.g., an acetyl group, a benzoyl group), or an aliphatic or aromatic sulfonyl group (e.g., a methanesulfonyl group, a benzenesulfonyl group).
L', L" and L"', which may be the same or different each represents -O-, -S- or
Among these groups, A is preferably a divalent group represented by
Of the compounds represented by the general formula (I), those represented by the general formula (I-a), (I-c) or (I-d) described below, and have a second-order reaction rate constant K₂ (80°C) in a reaction with p-anisidine in the range from 1×10^-1 ℓ/mol·sec to 1×10^-5 ℓ/mol·sec. are particularly preferred :

wherein R₁ has the same meaning as R₁ defined in the general formula (I); Link represents a single bond or - O-; Ar represents an aromatic group provided that it does not become a group useful as a photographic reducing group such as a hydroquinone derivative or a catechol derivative, as a result of reaction with an aromatic amine developing agent; R_a, R_b and R_e, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a carboxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an acylamino group, a sulfonamido group, an acyl group, an aliphatic or aromatic sulfonyl group, an alkoxycarbonyl group, a sulfo group, a hydroxy group, an acyloxy group, a ureido group, a urethane group, a carbamoyl group or a sulfamoyl group, wherein R_a and R_b or R_b and R_c may be connected to each other to form a 5-membered to 7-membered heterocyclic ring, which heterocyclic ring may further be substituted with a substituent, form a spiro ring or a bicyclo ring, or condensed with an aromatic ring; and Z₁ and Z₂ each represents a non-metallic atomic group necessary to form a 5-membered to 7-membered heterocyclic ring, which heterocyclic ring may further be substituted with a substituent, form a spiro ring or a bicyclo ring, or condensed with an aromatic ring.
The groups or rings in the formula (I) to (IV) and (I-a) to (I-b) may be substituted with a substituent such as groups recited for R_a, R_b and R_e, and/or a halogen atom.
In order to adjust the second-order reaction constant K₂ (80°C) in a reaction with p-anisidine in the range from 1×10^-1 ℓ/mol·sec to 1x10-⁵ ℓ/mol·sec in the compound represented by the general formula (I-a), (I-b), (I-c) or (I-d), especially in a case wherein Ar represents a carbocyclic series aromatic group in the general formula (I-a), one or more substituents may be appropriately selected. In this case, it is noted that the sum of the Ham- met's σ value of the individual substituents is preferably not less than 0.2, more preferably not less than 0.4, and further more preferably not less than 0.6, although it depends on the type of group represented by R₁.
In the case of adding the compound represented by the general formula (I) to the photographic light-sensitive material during the production thereof, the total number of carbon atoms included in the compound per se is preferably at least 13, and the more the carbon atoms present, the more preferred. On the other hand, in the case of adding the compound to a processing solution the total number of carbon atoms is usually not more than 13 in order to render the compounds water soluble.
It is preferred that the compound used according to the present invention does not decompose during development processing in order to attain the objects of the present invention.
In the general formula (II), Y preferably represents an oxygen atom, a sulfur atom, =N-R₄ or
wherein R₄, R₅ and R₆ each represents a hydrogen atom, an aliphatic group (e.g., a methyl group, an isopropyl group, a tert-butyl group, a vinyl group, a benzyl group, an octadecyl group, a cyclohexyl group), an aromatic group (e.g., a phenyl group, a pyridyl group, a naphthyl group), a heterocyclic (non-aromatic) group (e.g., a piperidyl group, a pyranyl group, a furyl group, a chromanyl group) an acyl group (e.g., an acetyl group, a benzoyl group) or an aliphatic or aromatic sulfonyl group (e.g., a methanesulfonyl group, a benzenesulfonyl group) wherein R₅ and R₆ may be connected to each other to form a cyclic structure.
In the compounds of the general formula (III) M represents an atom or an atomic group forming an inorganic salt (e.g., a salt of Li, Na, K, Ca, Mg, ammonium) or an organic salt (e.g., a salt of triethylamine, methylamine),

wherein R₁₅ and R₁₆, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, wherein R₁₅ and R₁₆ may be connected to each other to form a 5- membered to 7-membered ring; R₁₇, R₁₈, R₂₀, and R₂₁, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aliphatic or aromatic sulfonyl group, a ureido group, or a urethane group, provided that at least one of R₁₇ and R₁₈ and at least one of R₂₀ and R₂₁ each represents a hydrogen atom; R₁₉ and R₂₂ each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group; R₁₉ may further represent an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; wherein at least two of R₁₇, R₁₈ and R₁₉ may be connected to each other to form a 5-membered to 7-membered ring, and at least two of R₂₀, R₂₁ and R₂₂ may be connected to each other to form a 5-membered to 7-membered ring; R₂₃ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R₂₄ represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, an acyloxy group or an aliphatic or aromatic sulfonyl group; R₂₅ represents a hydrogen atom or an alkali-hydrolizable group; and R_io, R₁₁, R₁₂, R₁₃, and R₁₄, which may be the same or different, each represents a hydrogen atom, an aliphatic group (e.g., a methyl group, an isopropyl group, a tert-butyl group, a vinyl group, a benzyl group, an octadecyl group, a cyclohexyl group), an aromatic group (e.g., a phenyl group, a pyridyl group, a naphthyl, group), a heterocyclic group (e.g., a piperidyl group, a pyranyl group, a furyl group, a chromanyl group), a halogen atom (e.g., a chlorine atom, a bromine atom), -SR₂₆,

-OR₂₆,
(wherein, R₂₆ and R₂₇, which may be the same or different in the case of -NR₂₆R₂₇, each represents a hydrogen atom, an aliphatic group, an alkoxy group, or an aromatic group), an acyl group (e.g., an acetyl group, a benzoyl group), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, a butoxycarbonyl group, a cyclohexyloxycarbonyl group, an octyloxycarbonyl group), an aryloxycarbonyl group (e.g., a phenyloxycarbonyl group, a naphthyloxycarbonyl group), an aliphatic or aromatic sulfonyl group (e.g., a methanesulfonyl group, a benzenesulfonyl group), an aliphatic or aromatic sulfonamido group (e.g., a methanesulfonamido group, a benzenesulfo- namido group), a sulfamoyl group, a ureido group, a urethane group, a carbamoyl group, a sulfo group, a carboxy group, a nitro group, a cyano group, an alkoxyoxalyl group (e.g., a methoxyoxalyl group, an isobutoxyox- alyl group, an octyloxyoxalyl group, a benzyloxyoxalyl group), an aryloxyoxalyl group (e.g., a phenoxyoxalyl group, a naphthoxyoxalyl group), an aliphatic or aromatic sulfonyloxy group (e.g., a methanesulfonyloxy group, a benzenesulfonyloxy group), -P(R₂₆)₃,
-P(OR₂₆)₃, (wherein R₂₆ has the same meaning as defined above), or a formyl group.

In these groups, the group in which the sum of Hammet's σ values with respect to the -S0₂M group is at least 0.5 is preferred to better achieve the effect of the present invention.
In the case of adding the compound represented by the general formula (II) and (III) to the photographic material during the production thereof, the total number of carbon atoms of the compound is that which provides the compound non-diffusible. On the other hand, in the case of adding the compound (having no water-solubilizing group) to a processing solution the total number of carbon atoms is that which renders the compound water soluble.
Among the compounds represented by the general formulae (I), (II) and (III), those represented by the general formula (I) and (III) are preferred although preferred compounds in the individual general formula are those as described above.
Representative examples of the compounds represented by the general formula (I), (II) and (III) used in the present invention are illustrated below. (In the present invetion, the alkyl group in a formula, which does not have (t) or (i) means n-alkyl group.)
The compounds represented by the general formula (I), (II) or (III) can be synthesized according to the methods as described in EP 0,230,048A2, 0,258,662A2, and 0,255,722A2 and Japanese Patent Application (OPI) No. 229145/87 or methods analogous thereto.
Now, the compounds represented by the general formula (IV) are described in more detail below.
The aliphatic group, aromatic group and heterocyclic group represented by R₃₀, R₃₁ or R₃₅ each has the same meaning as defined for the aliphatic group, aromatic group and heterocyclic in the general formula (I), (II) or (III).
R₃₂, R₃₃ and R₃₄, which may be the same or different, each represents a straight chain, branched chain or cyclic alkyl group (e.g., a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a benzyl group, an octyl group, a cyclohexyl group, a hexadecyl group), an alkenyl group (e.g., a vinyl group, an allyl group), an aryl group (e.g., a phenyl group, a p-methylphenyl group, a 2-chlorophenyl group, a 3-methoxyphenyl group, a 2,4-dimethoxyphenyl group, a 4-hexadecyloxyphenyl group, a 3-pentadecylphenyl group, a 4-bromophenyl group, a naphthyl group), an alkoxy group (e.g., a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, a benzyloxy group, a hexadecyloxy group, a methoxyethoxy group), an alkenoxy group (e.g., an allyloxy group), or an aryloxy group (e.g., a phenoxy group, a 4-methoxyphenoxy group, a 3-chloro- phenoxy group, a 2-methylphenoxy group, a 2-tert-butyl-4-methylphenoxy group, a 4-hexadecyloxyphenoxy group, a naphthyloxy group).
Of the compounds represented by the general formula (IV), preferred compounds are these represented by the following general formula (IV-a), (IV-b), (IV-c), (IV-d), (IV-e) or (IV-f):

wherein R₄₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or
(wherein R₃₂, R₃₃, and R34 each has the same meaning as defined in the general formula (IV); R₄₂, R₄₃, R₄₄, R₄₅ and R₄₆, which may be the same or different, each represents a hydrogen atom, -W-R₃₁, an aliphatic group, an aromatic group, a heterocyclic group, a diacylamino group, a halogen atom, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a ureido group, a urethane group, a sulfamoyl group, a carbamoyl group, a cyano group, a nitro group, an aliphatic or aromatic carbonyloxy group, an aliphatic or aromatic sulfonyloxy group, a silyloxy group, or an imido group, - W-R₃₁ has the same meaning as defined in the general formula (IV), wherein R₄₁ and R₄₂ may be connected to each other to form a 5-membered to 7-membered ring, or two substituents of R₄₂ to R₄₆ which are present at the o-position to each other may be connected to each other to form a 5-membered to 7-membered ring, and wherein R₃₁ or R₃₅ when W represents
may be connected to a group present at the ortho position thereto to form a 5-membered to 7-membered ring.
The 5-membered to 7-membered ring described above may be a monocyclic ring, a condensed ring, a spiro ring, or a bicyclo ring, and the resulting condensed ring may be an alicyclic ring, an aromatic ring, a heterocyclic ring, or a heteroaromatic ring, and these rings may be substituted with one or more substituents.
R'₄₁ has the same meaning as R₃₅ defined in the general formula (IV), and R'₄₁ may be connected with R₄₁ or R₄₂ to form a 5-membered to 7-membered ring same as defined for R₄₁.
R₅₀ represents an aliphatic group, a heteroaromatic group, a heterocyclic group; R₅₁ represents a hydrogen atom, an aliphatic group, a heteroaromatic group or a heterocyclic group; and R₃₅ has the same meaning as defined in the general formula (IV), and R₅₀ and R₅₁ or R₅₀ and R₃₅ may be connected to each other to form a 5-membered to 7-membered ring which is the same as defined above for R₄₁.
Of the compounds represented by the general formulae (IV-a) to (IV-f), those represented by the general formula (IV-a) or (IV-f) are more preferred, and compounds represented by the general formula (IV-a1) to (IV- a8) and (IV-f1) described below are further more preferred.

wherein R₄₁ to R₄₆ each has the same meaning as defined in the general formula (IV-a), R'₄₁ and R'₄₂ to R'₄₆ each has the same meaning as defined for R₄₁ and R₄₂ to R₄₆ respectively, and each group may be connected to each other to form a 5-membered to 7-membered ring which is the same as defined in the general formula (IV-a); R₄₇ represents an aliphatic group, an aromatic group or a heterocyclic group; R₆₁ to R₆₄, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R_s5 and R₆₆, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an acyl amino group, or
wherein E₁ represents a non-metallic atomic group necessary to form a 5-membered to 7-membered ring; R₃₅ has the same meaning as defined in the general formula (IV-f); E represents a non-metallic atomic group necessary to form a 5-membered to 7-membered ring; and R₇₁ to R₇₄, which may be the same or different, each represents a hydrogen atom or an alkyl group.
In the case of adding the compound represented by the general formula (IV) to the photographic material during the production thereof, the total number of carbon atoms of the compound is that which provides the compound non-diffusible. On the other hand, in the case of adding the compound (having no water-solubilizing group) to a processing solution the total number of carbon atoms is that which renders the compound water soluble.
Now, the organic metal complexes used in the present invention are described in more detail below.
The organic metal complex which can be used in the present invention is characterized by containing copper, cobalt, nickel, palladium or platinum, as the central metal, and have at least one organic ligand having a bidentate or more conformation. As the central metal, nickel is particularly preferred. As the atom coordinated to the central metal, a nitrogen atom, a sulfur atom, an oxygen atom or a phosphorous atom is preferred.
Of the organic metal complexes used in the present invention, particularly preferred complexes are represented by the following general formula (V-a), (V-b), (V-c) or (V-d):

wherein M represents copper, cobalt, nickel, palladium or platinum; R₈₀ and R'₈₀, which may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or a hydroxy group, wherein R₈₀ and R'₈₀ may be connected to each other; R₈₁, R₈₂, R₈₃, R'₈₁, R'₈₂ and R'₈₃, which may be the same or different, to each represents a hydrogen atom, an alkyl group or an aryl group, wherein R₈₂ and R₈₃ or R'₈₂ and R'₈₃ may be connected to each other to form an aromatic ring or a 5-membered to 8-membered ring; R₈₄, R₈₅, R'₈₄ and R'₈₅, which may be the same or different, each represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an alkylamino group or an arylamino group; R₈₆, R₈₇, R₈₈, R₈₉, R₉₀, R'₈₆, R'₈₇, R'₈₈, R'₈₉ and R'₉₀, which may be the same or different, each represents a hydrogen atom, an alkyl group or an aryl group, wherein at least one of R₈₆ and R₈₇, R₈₉ and R₉₀, R'₈₆ and R'₈₇ and R'₈₉ and R'_9o may be connected to each other to form an aromatic ring or a 5-membered to 8-membered ring; X₁ represents a compound capable of coordinating to M; A_1' A₂, A'₁ and A'₂, which may be the same or different, each represents an oxygen atom, a sulfur atom, -NR₉₁-, a hydroxy group, an alkoxy group, an alkylthio group or
R₉₁ represents a hydrogen atom, an alkyl group, an aryl group, a hydroxy group or an alkoxy group; R₉₂ and R₉₃, which may be the same or different, each represents a hydrogen atom or an alkyl group; and A3 and A'₃ each represents an oxygen atom, a sulfur atom or -NH-.
In the general formulae (V-a), (V-b) , (V-c) and (V-d), an alkyl group or an alkyl moiety preferably has from 1 to 25 carbon atoms, and an aryl group or an aryl moiety preferably has from 6 to 25 carbon atoms.
Specific examples of the organic color fading preventing agents and the organic metal complexes used in the present invention are set forth below.
Compounds represented by the general formula (IV) and the complexes can be synthesized according to the methods as described in U.S. Patents 3,336,135, 3,432,300, 3,573,050, 3,574,627, 3,700,455, 3,764,337, 3,935,016, 3,982,944, 4,254,216 and 4,279,990, British Patents 1,347,556, 2,062,888, 2,066,975 and 2,077,455, Japanese Patent Application (OPI) Nos. 97353/85, 152225/77, 17729/78, 20327/78, 145530/79, 6321/80, 21004/80, 24141/83, 10539/84 and 67536/87, Japanese Patent Publication Nos. 31625/73 and 12337/79, or methods analogous thereto.
The compounds for use in the present invention which have low molecular weight or are easily soluble in water may be added to at least one processing solution such as a color developing solution, a bleaching solution, fixing solution, a blixing solution, water for washing and a stabilizing solution and carried over into the color photographic material during development processing of the color photographic material. However, it is preferred to incorporate the compounds into the color photographic material during the step of producing the color photographic material. In the latter case, the compounds are usually dissolved in a high-boiling point solvent (an oil) having a boiling point of at least 170°C at atmospheric pressure or a low-boiling point solvent, or a mixture of the above described oil and low-boiling solvent, and the solution is dispersed by emulsification in an aqueous solution of a hydrophilic colloid such as gelatin. The compounds for use in the present invention described above are preferably soluble in the high-boiling organic solvent. There is no particular restriction on the particle size of the emulsified dispersion particles of the compounds, but the particle size is preferably from 0.05 µm to 0.5 µm, particularly preferably from 0.1 µm to 0.3 µm. Further, it is particularly preferred that the compounds for use in the present invention be co-emulsified with coupler(s) to achieve the effects of the present invention. In this case, the ratio of oil/coupler is preferably from 0.00 (containing no oil) to 2.0 by weight ratio.
Each amount of the above described compounds of (1) and (2) is from 1 x1 0-2 mol to 10 mols, preferably from 3x10-² mols to 5 mols per mol of the coupler in the same layer. The molar ratio of the amount of the compound(s) of (1) to that of the compound(s) of (2) is preferably from 0.1 to 10.
Specific examples of the above described oil which can be used in the case of incorporating the compound used according to the present invention in the color photographic material include alkyl phthalates (e.g., dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate, monophenyl-p-tert-butylphenyl phosphate), citric acid esters (e.g., tributyl acetylcitrate), benzoic acid esters (e.g., octyl benzoate), alkylamides (e.g., diethyllaurylamide, dibutyllaurylamide),fatty acid esters (e.g., dibutoxyethyl succinate, diethyl azelate, dioctyl sebacate, trimesic acid esters (e.g., tributyl trimesate), compounds having an epoxy ring (e.g., those as described in U.S. Patent 4,540,657) phenols (e.g.,

ethers (e.g., phenoxyethanol, diethylene glyclol monophenyl ether).
Also, the low-boiling solvent which can be used as an auxiliary solvent in the case of incorporating the above described compounds used according to the present invention into the color photographic material preferably is an organic solvent having a boiling point of from about 30°C to about 150°C at atmospheric pressure and examples thereof include lower alkyl acetates (e.g., ethyl acetate, isopropyl acetate, butyl acetate), ethyl propionate, methanol, ethanol, secondary butyl alcohol, cyclohexanol, fluorinated alcohol, ethyl isobutyl ketone, ¡3-ethoxyethyl acetate, methyl cellosolve acetate, acetone, methylacetone, acetonitrile, dioxane, dimethylformamide, dimethylsulfoxide, chloroform, cyclohexane.
Furthermore, in place of the high-boiling organic solvent, an oily solvent for additives such as coupler(s), (including a solvent which is solid at room temperature, such as wax), as well as a latex polymer can be used. Additives themselves, such as a coupler, a color mixing preventing agent, an ultraviolet light absorbing agent, may be used as an oily solvent for dissolving the compounds for use in the present invention.
As the latex polymer as described above, there are latex polymers produced by using monomers such as acrylic acid, methacrylic acid, esters of these acids (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate), acrylamide, methacrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate) acrylonitrile, styrene, divinylbenzene, vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic acid esters (e.g., maleic acid methyl ester), N-vinyl-2-pyrrolidone, N-vinylpyridine, 2-vinylpyridine, and 4-vinylpyridine, singly or as a mixture of two or more.
In the case of dispersing the solution of the compound for use in the present invention alone or together with coupler(s) in an aqueous solution of a hydrophilic protective colloid, a surface active agent is usually used and examples of the surface active agent include saponin, sodium alkylsulfosuccinate, sodium alkylbenzenesulfonate.
The compounds used according to the present invention described above can be used in combination with a yellow coupler, a magenta coupler, or a cyan coupler. In these cases, it is particularly preferred, to achieve the effects of the present invention, to use the compounds in combination with a magenta coupler.
The coupler which is used in combination with the above described compounds may be 4-equivalent or 2-equivalent for silver ions, and also may be in the form of a polymer or an oligomer. Furthermore, the couplers which are used in combination with the above described compounds may be used singly or as a mixture of two or more kinds thereof.
Couplers which can be preferably used in the present invention are those represented by the following general formula (C-I), (C-II), (M-I), (M-II) or (Y);

wherein, R_1' R₄, and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic group; R₃and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group; R₅' represents a hydrogen atom, or a group represented by R₅ defined above; R₇ and R₉ each represents a substituted or unsubstituted phenyl group; R₈ represents a hydrogen atom, an aliphatic acyl group, an aromatic acyl group, an aliphatic sulfonyl group, or an aromatic sulfonyl group; R₁₀ represents a hydrogen atom or a substituent; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and Zb each represents a methine group, a substituted methine group, or =N-; and Y₁, Y₂, Y₃, Y₄, and Y₅ each represents a hydrogen atom, or a group capable of releasing upon a coupling reaction with the oxidation product of a color developing agent (hereinafter, the group is referred to as a releasing group).
In the general formulae (C-I) and (C-II) described above, R₂ and R₃ or R₅ and R₆ may be connected to each other to form a 5-membered, 6-membered, or 7-membered ring.
Furthermore, the coupler represented by the above described formula may form a dimer or a higher polymer through R_1' R₂, R₃ or Y₁; R₄, R₅, R₆ or Y₂; R₇, R_s, R₉ or Y₃; R₁₀, Za, Zb or Y₄; or Q or Y₅.
The aliphatic group described above is a straight chain, branched chain or cyclic alkyl, alkenyl, or alkynyl group.
Detailed description for the above-described couplers can be seen in the following U.S. Patents:

Couplers represented by the general formula (C-1):
- U.S. Patents 3,772,002, 4,564,590, 4,511,647 and 4,518,687
Couplers represented by the general formula (C-2):
- U.S. Patents 2,895,826, 4,557,999, 4,565,777, 4,124,396, 4,613,564, 4,327,173, 4,564,586 and 4,430,423
Couplers represented by the general formula (M-I):
- U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015
Couplers represented by the general formula (M-II):
- U.S. Patents 4,540,654 and 4,500,630
Couplers represented by the general formula (Y):
- U.S. Patents 4,622,287 and 4,623,616

Preferred specific examples of the cyan couplers represented by the general formulae (C-I) and (C-II) are illustrated below.
Preferred specific examples of the magenta couplers represented by the general formulae (M-I) and (M-II) are illustrated below.
Preferred specific examples of the yellow couplers represented by the general formula (Y) are illustrated below.
Examplexs of the couplers represented by the general formulae (C-I) to (Y) described above and others and synthesizing methods for them are described in the literature shown below.
The cyan couplers represented by the general formula (C-I) or (C-II) can be synthesized by the following known methods. For example, the cyan couplers represented by the general formula (C-I) can be synthesized by the methods as described in U.S. Patents 2,423,730 and 3,772,002, and the cyan couplers represented by the general formula (C-II) can be synthesized by the methods as described in U.S. Patents 2,895,826, 4,333,999 and 4,327,173.
The magenta couplers represented by the general formula (M-I) can be synthesized by the methods as described in Japanese Patent Application (OPI) Nos. 74027/74 and 74028/74, Japanese Patent Publication Nos. 27930/73 and 33846/78, U.S. Patent 3,519,429. Also the magenta couplers represented by the general formula (M-II) can be synthesized by the methods as described in U.S. Patent 3,725,067 and Japanese Patent Application (OPI) Nos. 162548/74, 171956/74 and 33552/85.
The yellow couplers represented by the general formula (Y) can be synthesized by the methods as described in Japanese Patent Application (OPI) No. 48541/79, Japanese Patent Publication No. 10739/83, U.S. Patent 4,326,024, Research Disclosure, No. 18053.
Each of these couplers is generally incorporated into a silver halide emulsion layer in an amount of from 2x10-³mol to 5x1 0-1 mol, and preferably from 1x10-² mol to 5x1 0-1 mol per mol of silver in the layer.
The compounds used according to the present invention are preferably employed in combination with the coupler represented by the general formula (C-I), (C-II), (M-I) or (M-II), more particularly with the magenta coupler represented by the general formula (M-I) or (M-II) in order to achieve the effects of the present invention.
In the case of employing the magenta coupler represented by the general formula (M-II) wherein Za represents -N=, Z_b represents a substituted methine group and Y₄ represents a chlorine atom in combination with the compound represented by the general formula (I-c) wherein Z₁ represents an atomic group necessary to form a 2-pyrazoline ring, the effect of improving light-fastness of magenta dye is relatively small in comparison with cases using other compounds of the general formula (I-C).
When the color photographic material according to the present invention contains dye(s) and ultraviolet light absorbing agent(s) in the hydrophilic colloid layer(s) thereof, these additives may be mordanted for example, by a cationic polymer.
The color photographic material according to the present invention may further contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, as a color fog preventing agent.
The color photographic material according to the present invention may contain ultraviolet light absorbing agent(s) in the hydrophilic colloid layer as described above. Examples of the ultraviolet light absorbing agents include aryl group-substituted benzotriazole compounds (e.g., those as described in U.S. Patent 3,533,794), 4-thiazolidone compounds (e.g., those as described in U.S. Patents 3,314,794 and 3,352,681), benzophenone compounds (e.g., those as described in Japanese Patent Application (OPI) No. 2784/71), cinnamic acid ester compounds (e.g., those as described in U.S. Patents 3,705,805 and 3,707,375), butadiene compounds (e.g., those as described in U.S. Patent4,045,229), and bisphenol derivatives (e.g., those as described in U.S. Patent 3,700,455). Furthermore, ultraviolet light absorptive couplers (e.g., a-naphtholic cyan dye forming couplers) or ultraviolet light absorptive polymers may be used as ultraviolet light absorbing agents. These ultraviolet light absorbing agents may be mordanted in a specific layer.
The color photographic material according to the present invention may contain water-soluble dyes as filter dyes or for irradiation prevention or other various purposes in the hydrophilic colloid layers. Examples of such water-soluble dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. In these dyes, oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful.
As the binder or protective colloids which can be used for the emulsion layers of the color photographic material according to the present invention, gelatin is advantageously used but other hydrophilic colloids can be used alone or together with gelatin.
As gelatin, lime-treated gelatin or acid-treated gelatin can be used in the present invention. Details of the production of gelatin are described in Arther Weiss, The Macromolecular Chemistry of Gelatin, published by Academic Press, 1964.
For the silver halide emulsion layers of the color photographic material according to the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride is used as the silver halide.
There is no particular restriction on the average grain size (the grain size being defined as the diameter of the grains when the grain has a spherical or a nearly spherical form and as the length of the edge when the grain has a cubic form, and being averaged based on the projected area of the grains) of the silver halide grians in the photographic emulsions but it is preferred that the grain size be not more than 2 f..lm.
The grain size distribution may be narrow or broad, but a monodispersed silver halide emulsion having a coefficient of variation of not more than 15% is preferred.
The silver halide grains in the photographic emulsion layers may have a regular crystal form such as cubic, octahedral, oran irregular crystal form such as spherical, tabular, or may have a composite form of these crystal forms. Also, a mixture of grains having various crystal forms may be used. Of these emulsions, the use of a photographic emulsion of regular crystal form is preferred.
Further, a silver halide emulsion wherein tabular silver halide grains having a diameter/thickness ratio of at least 5 accounts for at least 50% of the total projected area of the silver halide grains may be used in the present invention.
The silver halide grains used in the present invention may have a composition or structure inside the grain which is different from that on the surface layer thereof. Also, the silver halide grains may be of the type that latent images are formed mainly on the surface thereof or of the type that latent images are formed mainly in the interior thereof.
During the formation or physical ripening of the silver halide grains, a cadmium salt, a zinc salt, a thallium salt, a lead salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, may exist in the system.
Silver halide emulsions are usually chemically sensitized.
The silver halide emulsions used in the present invention can further contain various kinds of compounds for preventing the occurrence of fog or for stabilizing photographic performance during the production, storage and/or photographic processing of color photographic materials. Examples of such compounds include the compounds known as antifoggants or stabilizers such as azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular, 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes (e.g., triazaindenes, tetraazaindenes, in particular, 4-hydroxy-substituted (1,3,3a,7)tetraazaindene), pentaazaindenes; benzenethiosulfonic acid, benzenesulfin- ic acid, benzenesulfonic acid amide.
The present invention can be applied to multilayer multicolor photographic materials having at least two photographic emulsion layers each having different spectral sensitivity on a support. A multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The disposition order of these photographic emulsion layers can be optionally selected according to the purpose for which the photographic material is used. Usually, a red-sensitive emulsion layer contains a cyan-forming coupler, a green-sensitive emulsion layer contains a magenta-forming coupler, and a blue-sensitive emulsion layer contains a yellow-forming coupler. Other combinations may be used, if desired.
As the support used in the present invention, there are those conventionally employed in photographic light-sensitive materials, for example, cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, laminates of these films, thin glass films, papers. Paper coated with baryta or an α-olefin polymer, in particular, a polymer of an α-olefin having 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethy- lenebutene copolymer, and a support such as a plastic film, having a roughened surface for improving the adhesion with other polymers as described in Japanese Patent Publication No. 19068/72 give good results. Also, a resin hardenable by the irradiation of ultraviolet rays can be used.
According to the purpose of the color photographic material, a transparent support or an opaque support may be used. Also, a colored transparent support containing dyes or pigments can also be used.
As an opaque support used in the present invention, there are papers which are opaque by themselves and transparent films which were opacified by the incorporation of dyes or pigments such as titanium oxide. Also, a plastic film surface-treated by the method as described in Japanese Patent Publication No. 19068/72 and further papers or plastic films rendered completely light shielding by the addition of carbon black, dyes, can be used.
A subbing layer is usually provided on the support. Furthermore, for improving the adhesive property, a pretreatment such as a corona discharging treatment, an ultraviolet irradiation treatment, a flame treatment, may be applied to the surface of the support.
As a color photographic light-sensitive material which can be used for making the color photograph according to the present invention, an ordinary color photographic light-sensitive material, in particular, a color photographic light-sensitive material for color print is preferred, and color photographic light-sensitive materials of color photographic systems (in particular, color diffusion transfer photographic systems) as described in U.S. Patents 3,227,550, 3,227,551 and 3,227,552, and U.S. Preliminary Published Patent B351,673, may be used.
For obtaining dye images by a conventional photographic process, it is necessary to apply color photographic development processing after imagewise exposure. Color photographic development processing fundamentally includes the steps of color development, bleaching and fixing. In this case, two steps of bleaching and fixing may be performed by one step (bleach-fixing).
Furthermore, a combination of color development, first fixing, and bleach-fixing can be employed in the present invention. The color development processing step may include, if necessary, various steps of pre-hardening, neutralization, first development (black-and-white development), image stabilization, washing with water. The processing temperature is generally 18°C or more, and preferably in the range from 20°C to 60°C. In particular, recently the range of from 30°C to 60°C is used.
A color developing solution is an aqueous alkaline solution containing an aromatic primary amine color developing agent and having a pH of at least 8, preferably from 9 to 12.
After the fixing or bleach-fixing step, a water washing process is usually performed, but a simple so-called "stabilization process" may be substituted in place of the waterwashing process substantially without employing a water washing step.
Preferred examples of the aromatic primary amine color developing agent are p-phenylenediamine derivatives and specific examples thereof are described below:

D-1 N,N-Diethyl-p-phenylenediamine
D-2 2-Amino-5-diethylaminotoluene
D-3 2-Amino-5-(N-ethyl-N-laurylamino)toluene
D-4 4-(N-ethyl-N-((3-hydroxyethyl)amino)aniline
D-5 2-Methyl-4-[4-N-ethyl-N-(β-hydroxyethyl)amino]aniline
D-6 N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline
D-7 N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide
D-8 N,N-Dimethyl-p-phenylenediamine
D-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
D-10 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline
D-11 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylani line

Also, these p-phenylenediamine derivatives may be in the form of salts thereof, such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates. The above described compounds are described, for example, in U.S. Patents 2,193,015, 2,552,241, 2,566,271, 2,592,364, 3,656,950 and 3,698,525. The amount of the aromatic primary amine color developing agent is from about 0.1 g to about 20 g, and preferably from about 0.5 g to about 10 g per liter of color developing solution.
The color developing solution used in the present invention may contain hydroxylamines as conventionally known.
The processing temperature of the color developing solution is preferably from 30°C to 50°C, and more preferably from 33°C to 42°C. Also, the amount of a replenisher for the color developing solution is from 30 ml to 2,000 ml, and preferably from 30 ml to 1,500 ml per square meter of color photographic material. The amount of the replenisher is, however, preferably as low as possible from the viewpoint of reducing the amount of waste liquid.
Also, when benzyl alcohol exists in the color developing solution, the amount thereof is preferably not more than 2.0 mi/liter, and more preferably not more than 0.5 ml/liter. A color developing solution containing no benzyl alcohol is most preferred. The time for color development is preferably within 2 minutes and 30 seconds, more preferably from 10 seconds to 2 minutes and 30 seconds, and most preferably from 45 seconds to 2 minutes.
The compounds of (1) and (2) may be applied to a silver halide color photographic material after imagewise exposure. The application can be conducted by incorporating the compounds into at least one of color photographic processing solutions such as a developing solution, a bleaching solution, a fixing solution, a blixing solution, water for washing or water specifically provided for applying the compounds to the photographic material, or a stabilizing solution. It is also possible to incorporate these compounds separately into two or more solution.
The compounds are preferably contained in a developing solution. It is also possible to apply the compounds after developing process using an aqueous solution containing the compounds.
Each concentration of the compounds (1) and (2) in the processing solution is preferably from 1 x 10^-5 to 1 moi/f, and the molar ratio of the concentration of the compound (1) to that of compound (2) is from 0.1 to 10.
According to the present invention color photographic light-sensitive materials are provided which exhibit remarkable improvement in preservability even when the composition of the processing solution is changed due to processing with a processing solution which provides a large amount of its components to the color photographic material, such as a processing solution of a running state, a processing solution of reduced amount of washing water or without employing a water washing step, a color developing solution containing substantially no benzyl alcohol, or other processing solutions which impose a burden on color development.
In accordance with the present invention color photographs excellent in fastness of color images are obtained. In particular, by the use of the color photographic light-sensitive material according to the present invention, color photographs are obtained in which, the three color balance of a yellow dye, a magenta dye and a cyan dye is maintained and the coloration of white background is exceptionally low even when they are preserved for a long period of time.
The present invention will be described in more detail with reference to the following examples.

EXAMPLE 1

On a paper support, both surfaces of which were laminated with polyethylene, a first layer (the undermost layer) to a seventh layer (the uppermost layer) as shown in Table A below were coated in this order to prepare a color photographic light-sensitive material.
In addition, the following spectral sensitizing dyes were used for the above described silver halide emulsion layers.

For the Blue-Sensitive Emulsion Layer:
(2x10-4 mol per mol of silver halide)
For the Green-Sensitive Emulsion Layer:
(2.5x10^-4 mol per mol of silver halide)
For the Red-Sensitive Emulsion Layer:
(2.5x10^-4 mol per mol of silver halide)

The compounds used for preparing the above described color photographic light-sensitive material were as follows.

Solvent (a):
- (iso-C₉H₁₉O)̵₃P=O
Color Mixing Preventing Agent (b):
Solvent (c):
- (C₈H₁₇O)̵₃P=O and
  in a 2:1 mixture (weight ratio).
Ultraviolet Light Absorbing Agent (d):
and
in a 1:5:3 mixture (molar ratio).
Solvent (e):
Color Image Stabilizer (f):
and
in a 1:3:3 mixture (molar ratio).

Furthermore, the following dyes were used for the emulsion layers as irradiation preventing dyes.

For the Green-Sensitive Emulsion Layer:
For the Red-Sensitive Emulsion Layer:

Using the combinations of couplers and the compounds employed according to the present invention as shown in Table 1 below samples were prepared. The additives were dissolved into the solutions containing the coupler and then the solutions thus obtained were incorporated into the silver halide emulsion.
These samples were exposed through an optical wedge and then subjected to development processing according to the following steps.
The compositions of the processing solutions used were as follows.

Color Developing Solution

Bleach-Fixing Solution

The compositions of the processing solutions used were almost in an equilibrium state since the development processing was conducted while performing normal replenishing using an ordinary roller transport type developing solution processer.
With each sample thus-processed, a cyan, yellow and magenta reflection density was measured using a Fuji self-recording type densitometer (made by Fuji Photo Film Co., Ltd.). Then, each sample was subjected to a fading test using a fluorescent lamp tester (15,000 lux) for 30 days.
The results thus-obtained are shown in Table 1 below.
From the results shown in Table 1, it can be seen that the greatly improved effect on light fastness is observed by the combination of the compounds used according to the present invention in multilayer samples.

EXAMPLE 2

A color photographic light-sensitive material (Sample G) was prepared as follows.
A multilayer color photographic light-sensitive material in which Layer 1 to Layer 11 have the following layer structure on a paper support, both surfaces of the paper support having been laminated with polyethylene, was prepared. In this case, the polyethylene coating on the Layer 1 side of the support contained titanium dioxide as a white pigment and a small amount of ultramarine as a bluish dye.

Construction of Layers

The composition of each layer is shown below. The coating amounts of the components are described in the unit of g/m². With respect to silver halide, the coating amount is indicated in terms of a silver coating amount.

Layer 1: Antihalation Layer:
Layer 2: Low-Speed Red-Sensitive Layer:
Layer 3: High-Speed Red-Sensitive Layer:
Layer 4: Interlayer:
Layer 5: Low-Speed Green-Sensitive Layer:
Layer 6: High-Speed Green-Sensitive Layer:
Layer 7: Yellow Filter Layer:
Layer 8: Low-Speed Blue-Sensitive layer:
Layer 9: High-Speed Blue-Sensitive Layer:
Layer 10: Ultraviolet Light Absorbing Layer:
Layer 11: Protective Layer:

The compounds used for the color photographic light-sensitive material were as follows.
Further, in the same manner as described for Sample G above, except adding the compounds according to the present invention to each Layer 5 and Layer 6 of Sample G as shown in Table 2, other samples were prepared. The additives were dissolved into the solution containing the coupler and then the solutions thus obtained were incorporated into the silver halide emulsion.
The samples thus-prepared were exposed through an optical wedge and subjected to development processing according to the following processing steps.
The compositions for the processing solutions used were as follows.

First Developing Solution

Color Developing Solution

Bleach-Fixing Solution

The magenta reflection density (stain) at the non-imaged portion of each sample thus processed was measured and then the magenta reflection density (stain) at the non-imaged portion thereof was measured again after allowing the sample to stand for 3 days at 80°C and 70% RH and after allowing the sample to stand for 80 days at room tesmperature. The increase in stain from one hour after processing is shown in Table 2 below.
Further, in order to evaluate light fastness of each sample, a magenta reflection density was measured using a Fuji self-recording type densitometer. Then, each sample was subjected to a fading test using a fluorescent lamp tester (15,000 lux) for 30 days. The results thus-obtained are also shown in Table 2 below.
From the results shown in Table 2, it can be seen that the combination of the compounds used according to the present invention is extremely effective not only for preventing color (magenta) stain due to the preservation after the development processing but also for improving light fastness of magenta dye.

EXAMPLE 3

The following First layer to Fourteenth layer were coated on a paper support, both surfaces of which were laminated with polyethylene to prepare a multilayer color photographic light-sensitive material. The polyethylene laminated on the First layer side of the support contained titanium dioxide as a white pigment and a small amount of ultramarine as a bluish dye.

Construction of Layers

The composition of each layer is shown below. The coating amounts of the components are described in the unit of g/m². With respect to silver halide, the coating amount is indicated in terms of silver coating amount.

First Layer: Antihalation Layer
Second Layer: Intermediate Layer
Third Layer: Low-Sensitive Red-sensitive Layer
Fourth Layer: High-Sensitive Red-sensitive Layer
Fifth Layer: Intermediate Layer
Sixth layer: Low-Sensitive Green-sensitive Layer
Seventh Layer: High-Sensitive Green-sensitive Layer
Eighth Layer: Intermediate Layer Same as Fifth Layer
Ninth Layer: Yellow Filter Layer
Tenth Layer: Intermediate Layer Same as Fifth Layer
Eleventh Layer: Low-Sensitive Blue-sensitive Layer
Twelfth Layer: High-Sensitive Blue-sensitive Layer
Thirteenth Layer: Ultraviolet Light Absorbing Layer
Fourteenth Layer: Protective Layer

A specific example of the preparation of the silver halide emulsions used herein, except that used in Fourteenth layer, is illustrated below.
An aqueous solution of potassium bromide and an aqeuous solution of silver nitrate were added simultaneously to a gelatin aqueous solution containing 0.3 g/molAg of 3,4-dimethyl-1,3-thiazoiine-2-thion over about 20 minutes at 75°C while vigorously stirring, to obtain a monodispersed octahedral silver bromide emulsion having an average grain size of about 0.40 µm. 6 mg/molAg of sodium thiosulfate and 7 mg/molAg of chloroauric acid tetrahydrate were added thereto and the emulsion was heated to 75°C for 80 minutes to accomplish chemical sensitization; While the thus-obtained silver bromide particles were used as core particles, the particles were further grown under the same precipitation condition as above to obtain a monodispersed octahedral core/shell type silver bromide having an average grain size of about 0.7 µm. The coefficient of variation of the grain size was about 10%.
1.5 mg/molAg of sodium thiosulfate and 1.5 mg/molAg of chloroauric acid tetrahydrate were added to the emulsion, and the emulsion was heated to 60°C for 60 minutes to accomplish chemical sensitization, thus an internal latent image type silver halide emulsion was obtained.
To each light-sensitive layer, nucleating agent (N-I-9) and Nucleating accelerator (ExZS-1) were added in amounts of 1x10^-3 wt% and 1 xl 0-2 wt%, respectively, based on the amount of silver halide.
To each layer, emulsifying dispersing aids (Alkanol XC (Du Pont) and sodium alkylbenzenesulfonate, and coating aids (succinic acid ester and Magefac F-120 (Dai Nippon Ink and Chemical Co., Ltd.)) were added. Furthermore, to the layers containing silver halide or colloidal silver, stabilizers (Cdp-15, 16, 17) were added. The thus-obtained photographic light-sensitive material was designated Sample H.
The compounds used in Example 3 are illustrated below.

(H-1) 1,2-Bis(vinylsulfonylacetamido)ethane
Cpd-8 Polyethylacrylate

ExM-1 M-25

(Solv-1) Di(2-ethylhexyl)phthalate
(Solv-2) Trinonylphosphate
(Solv-3) Di(3-methylhexyl)phthalate
(Solv-4) Tricresylphosphate
(Solv-5) Dibutylphthalate
(Solv-6) Trioctylphosphate
(Solv-7) Dioctylsebacate

Further, in the same manner as described for Sample H above, except using the combination of the compounds according to the present invention in the Sixth Layer and Seventh Layer of Sample H as shown in Table 3 below, other samples were prepared. The additives were dissolved into the solutions containing the coupler and then the solutions thus obtained were incorporated into the silver halide emulsion.
The samples thus-obtained were exposed to light through an optical wedge, and then processed according to the following Processing A.

Processing A

In the water washing steps, water was supplied to the water washing tank (2), and the overflow was introduced to the water washing tank (1) (the so-called countercurrent replenishing system).
The compositions of the processing solutions used were as follows.
(pH was adjusted with potassium hydroxide or hydrochloric acid.)
(pH was adjusted with aqueous ammonia or hydrochloric acid.)

Washing Water

Pure water was used.
The term "pure water" used herein means the water produced by processing city water with an ion exchange process whereby the cation concentration and the anion concentration (except hydrogen ion and hydroxide ion) were reduced to 1 ppm or less.
The magenta reflection density of each sample was measured using a Fuji self-recording type densitometer. Then, each sample was subjected to a fading test using a fluorescent lamp tester (15,000 lux) for 30 days. The results thus-obtained are shown in Table 3 below.
It can be seen from the results shown in Table 3 that almost equivalent results to those in Example 1 are obtained. Specifically, the extent of the effect on the improvement in light fastness based on the combination of the compounds used according to the present invention is extremely large in spite of the difference in the layer compositions of photographic light-sensitive material.

Claims

1. A silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer, wherein the silver halide color photographic material contains

(1) at least one compound represented by the general formula (I) or (II) and at least one compound represented by the general formula (III), each compound of the formula (I), (II), and (III) including dimers or higher polymers containing at least one moiety derived from the compounds:

wherein R₁ and R₂ each represents an aliphatic group, an aromatic group or a heterocyclic group; X represents a group capable of being released upon a reaction of A with an aromatic amine developing agent; A represents a group capable of reacting with an aromatic amine developing agent to form a chemical bond; n represents 0 or 1; if n is 0, X represents a halogen atom; B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or an aliphatic or aromatic sulfonyl group; Y represents a group capable of accelerating the addition of an aromatic amine developing agent to the compound represented by the general formula (II); wherein R₁ and X, or Y and R₂ or B may be connected to each other to form a cyclic structure; M represents an atom or an atomic group forming an inorganic salt or an organic salt,

wherein R₁₅ and R₁₆, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, wherein R₁₅ and R₁₆ may be connected to each other to form a 5-membered to 7-membered ring; R₁₇, R₁₈, R₂₀ and R₂₁ which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aliphatic or aromatic sulfonyl group, a ureido group, or a urethane group, provided that at least one of R₁₇ and R₁₈ and at least one of R₂₀ and R₂₁ each represents a hydrogen atom; R₁₉ and R₂₂ each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group; R₁₉ may further represent an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; wherein at least two of R₁₇, R₁₈ and R₁₉ may be connected to each other to form a 5-membered to 7-membered ring, and at least two of R₂₀, R₂₁ and R₂₂ may be connected to each other to form a 5-membered to 7- membered ring; R₂₃ represents a hydrogen atom, an aliphatic group, an aromatic group ora heterocyclic group; R₂₄ represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, an acyloxy group or an aliphatic or aromatic sulfonyl group; R₂₅ represents a hydrogen atom or an alkali-hydrolizable group; and R_io, R₁₁, R₁₂, R₁₃, and R₁₄, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, -SR₂₆, -OR₂6,

(wherein R₂₆ and R₂₇, which may be the same or different in the case of -NR₂₆R₂₇, each represents a hydrogen atom, an aliphatic group, an alkoxy group, or an aromatic group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic sulfonamido group, a sulfamoyl group, a ureido group, a urethane group, a carbamoyl group, a sulfo group, a carboxy group, a nitro group, a cyano group, an alkoxyoxalyl group, an aryloxyoxalyl group, an aliphatic or aromatic sulfonvloxv group, -P(R₂₆)₃,

-P(OR₂₆)₃, (wherein R₂₆ has the same meaning as defined above), or a formyl group; and

(2) at least one compound selected from the group consisting of organic color fading preventing agents represented by the general formula (IV) and dimers or higher polymers containing at least one moiety derived from the agents, organic metal complexes containing copper, cobalt, nickel, palladium or platinum as the central metal and having at least one organic ligand having at least one atom which coordinates with the central atom and dimers or higher polymers containing at least one moiety derived from the complexes:

wherein R₃₀ represents an aliphatic group, an aromatic group or a heterocyclic group; R₃₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or

R₃₂, R₃₃ and R₃₄, which may be the same or different, each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group or an aryloxy group; W represents -O-, -S- or

R₃₅ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy-radical group or a hydroxy group; wherein R₃₀ and R₃₁ or R₃₅ and R₃₀ or R₃₁ may be connected to each other to form a 5-membered to 7-membered ring.

2. The silver halide color photographic material of claim 1, wherein the compound represented by the general formula (I) or (II) has a second-order reaction rate constant K₂ (80°C) in a reaction with p-anisidine in a range from 1.0 I/mol.s to 1x10-⁵ I/mol.s.

3. The silver halide color photographic material of claim 1, wherein the group represented by X in the general formula (I) is a group connected to A through an oxygen atom, a sulfur atom, or a nitrogen atom, or a halogen atom.

4. The silver halide color photographic material of claim 1, wherein the group represented by A in the general formula (I) is a group containing an atom of low electron density selected from

wherein L represents a single bond, an alkylene group, -0-, -S -,

Y has the same meaning as defined in the general formula (II); Y' has the same meaning as defined for Y; R' and R", which may be the same or different, each represents -L"'-R_o; R_o has the same meaning as defined for R₁; R represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or an aliphatic or aromatic sulfonyl group; and L', L" and L"' each represents -0-, - S- or

5. The silver halide color photographic material of claim 4, wherein A represents

or

6. The silver halide color photographic material of claim 1, wherein the compound represented by the general formula (I) is selected from compounds represented by the following general formula (I-a), (I-b), (I-c) and (I-d) and has a second-order reaction rate constant K₂ (80°C) in a reaction with p-anisidine in the range of from 1x10^-1 l/mol.s to 1x10^-5 I/mol.s:

wherein R₁ has the same meaning as R₁ defined in the general formula (I); Link represents a single bond or -0-; Ar represents an aromatic group provided that it does not become a group useful as a photographic reducing group as a result of reaction with an aromatic amine series developing agent; R_a, R_b and R_c, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a carboxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an acylamino group, a sulfonamido group, an acyl group, an aliphatic or aromatic sulfonyl group, an alkoxycarbonyl group, a sulfo group, a hydroxyl group, an acyloxy group, a ureido group, a urethane group, a carbamoyl group or a sulfamoyl group, wherein R_a and R_b, or R_b and R_e may be connected to each other to form a 5-membered to 7-membered hetero ring, which hetero ring may be further substituted with a substituent, or form a spiro ring, a bicyclo ring, or may be fused with an aromatic ring; Z₁ and Z₂ each represents a non-metallic atomic group necessary for forming a 5-membered to 7-membered hetero ring, which hetereo ring may be further substituted with a substituent, or form a spiro ring, a bicyclo ring, or may be fused with an aromatic ring.

7. The silver halide color photographic material of claim 6, wherein the compound represented by the general formula (I-a), (I-b), (I-c) or (I-d) has a total number of at least 13 carbon atoms.

8. The silver halide color photographic material of claim 1, wherein the group represented by Y in the general formula (II) is an oxygen atom, a sulfur atom, =N-R₄ or

wherein R₄, R₅ and R₆ each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or an aliphatic or aromatic sulfonyl group, wherein R₅ and R₆ may be connected to each other to form a cyclic structure.

9. The silver halide color photographic material of claim 1, wherein the compound represented by the general formula (IV) is a compound represented by the following general formula (IV-a), (IV-b), (IV-c), (IV-d), (IV- e) or (IV-f):

wherein R₄₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or

(wherein R₃₂, R₃₃, and R34 each has the same meaning as defined in the general formula (IV)); R₄₂, R₄₃, R₄₄, R₄₅ and R₄₆ which may be the same or different, each represents a hydrogen atom, -W-R₃₁, an aliphatic group, an aromatic group, a heterocyclic group, a diacylamino group, a halogen atom, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a ureido group, a urethane group, a sulfamoyl group, a carbamoyl group, a cyano group, a nitro group, an aliphatic or aromatic carbonyloxy group, an aliphatic or aromatic sulfonyloxy group, a silyloxy group, or an imido group, -W-R₃₁ has the same meaning as defined in the general formula (IV), wherein R₄, and R₄₂ may be connected to each other to form a 5-membered to 7-membered ring, or two substituents of R₄₂ to R₄₆ which are present at the o-position to each other may be connected to each other to form a 5-membered to 7-membered ring, or R₃₁ or R₃₅ when W represents

may be connected to a group present at the ortho-position thereto to form a 5-membered to 7-membered ring, R'₄₁ has the same meaning as R₃₅ defined in the general formula (IV), wherein R'₄₁ may be connected with R₄₁ or R₄₂ to form a 5-membered to 7-membered ring which is the same as defined for R₄₁, R₅₀ represents an aliphatic group, a heteroaromatic group, a heterocyclic group, R₅₁ represents a hydrogen atom, an aliphatic group, a heteroaromatic group or a heterocyclic group, and R₃₅ has the same meaning as defined in the general formula (IV), and R₅₀ and R₅₁ or R₅₀ and R₃₅ may be connected to each other to form a 5-membered to 7-membered ring which is the same as defined above for R₄₁.

The silver halide color photographic material of claim 9, wherein the compound represented by the general formula (IV-a) or (IV-f) is a compound represented by the following general formula (IV-a1), (IV-a2), (IV- a3), (IV-a4), (IV-a5), (IV-a6), (IV-a7), (IV-a8) or (IV-f1):

wherein R₄₁ to R₄₆ each has the same meaning as defined in the general formula (IV-a), R'₄₁ and R'₄₂ to R'₄₆ each has the same meaning as defined for R₄₁ and R₄₂ to R₄₆ respectively, and each substituent may be connected to each other to form a 5-membered to 7-membered ring which is the same as defined in the general formula (IV-a); R₆₁ to R64 which may be the same or different, each represents a hydrogen atom, an aliphatic group,an aromatic group or a heterocyclic group; R₆₅ and R₆₆, which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an acylamino group or

wherein E₁ represents a non-metallic atomic group necessary to form a 5-membered to 7-membered ring; R₃₅ has the same meaning as defined in the general formula (IV-f); E represents a non-metallic atomic group necessary to form a 5-membered to 7-membered ring; and R₇₁ to R₇₄, which may be the same or different, each represents a hydrogen atom or an alkyl group.

11. The silver halide color photographic material of claim 1, wherein the central metal of the organic metal complex is nickel.

12. The silver halide color photographic material of claim 1,wherein the organic metal complex is a complex represented by the following general formula (V-a), (V-b), (V-c) or (V-d):

wherein M represents copper, cobalt, nickel, palladium or platinum; R₈₀ and R'₈₀, which may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or a hydroxy group, wherein R₈₀ and R'₈₀ may be connected to each other; R₈₁, R₈₂, R₈₃, R'₈₁, R'₈₂ and R'₈₃, which may be the same or different, each represents a hydrogen atom, an alkyl group or an aryl group, wherein R₈₂ and R₈₃ or R'₈₂ and R'₈₃ may be connected to each other to to form an aromatic ring or a 5-membered to 8-membered ring; R₈₄, R₈₅, R'₈₄ and R'₈₅, which may be the same or different, each represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an alkylamino group or an arylamino group; R₈₆, R₈₇, R₈₈, R₈₉, R₉₀, R'₈₆, R'₈₇, R'₈₈, R'₈₉ and R'₉₀ which may be the same or different, each represents a hydrogen atom, an alkyl group or an aryl group, wherein at least one of R₈₆ and R₈₇, R₈₉ and R₉₀, R'₈₆ and R'₈₇ and R'₈₉ and R'₉₀ may be connected to each other to form an aromatic ring or a 5-membered to 8-membered ring; X₁ represents a compound capable of coordinating to M; A₁, A₂, A'₁ and A'₂, which may be the same or different, each represents an oxygen atom, a sulfur atom, -NR₉₁-, a hydroxy group, an alkoxy group, an alkylthio group or

R₉₁ represents a hydrogen atom, an alkyl group, an aryl group, a hydroxy group or an alkoxy group; R₉₂ and R₉₃, which may be the same or different, each represents a hydrogen atom or an alkyl group; and A3 and A'₃ each represents an oxygen atom, a sulfur atom or -NH-.

13. The silver halide color photographic material of claim 1, wherein the color photographic material contains at least one of a yellow coupler, a magenta coupler and a cyan coupler.

14. The silver halide color photographic material of claim 13, wherein the coupler is selected from those represented by the following general formula (C-I), (C-II), (M-I) , (M-II) or (Y):

wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group; R₅' represents a hydrogen atom, ora a group represented by R₅ defined above; R₇ and R₉ represents a substituted or unsubstituted phenyl group; R₈ represents a hydrogen atom, an aliphatic acyl group, an aromatic acyl group, an aliphatic sulfonyl group, or an aromatic sulfonyl group; R₁₀ represents a hydrogen atom or a substituent; Q represents a substituted or unsubstituted N-phenyl-carbamoyl group; Za and Zb each represents a methine group, a substituted methine group, or =N-; and Y₁, Y₂, Y₃ and Y₅ each represents a hydrogen atom, or a group capable of being released upon a coupling reaction with the oxidation product of a color developing agent; wherein R₂ and R₃ or R₅ and R₆ may be connected to each other to form a 5-membered to 7-membered ring; or R₁, R₂, R₃ or Y₁; R₄, R₅, R₆ or Y₂; R₇, R₈, R₉ or Y₃; R₁₀, Z_a, Z_b or Y₄; and Q or Z₅ ech may form a dimer or a higher polymer.

15. The silver halide color photographic material of claim 1, wherein each amount of said at least one compound of (1) and said at least one compound of (2) is from 1 x 10-²to 10 mol per mol of the coupler in the same layer.

16. The silver halide color photographic material of claim 15, wherein the molar ratio of the amount of said at least one compound of (1) and said at least one compound of (2) is from 0.1 to 10.

17. The silver halide color photographic material of claim 1, wherein the compound(s) of (1) and the compound(s) of (2) are incorporated in at least one hydrophilic colloidal layer in the photographic material.

18. The silver halide color photographic material of claim 17, wherein said hydrophilic colloidal layer is a silver halide emulsion layer.

19. A method for producing color images which comprises imagewise exposing a silver halide color photographic material containing at least one dye image forming coupler and subjecting the photographic material exposed to a color photographic processing in the presence of at least one compound of (1) and at least one compound of (2) as defined in claim 1.

20. The method of claim 19, wherein said compounds are incorporated in at least one of a developing solution, a bleaching solution, a fixing solution, a blixing solution, a stabilizing solution and washing water.

21. The method of claim 20, wherein each concentration of said at least one compound of (1) and said at least one compound of (2) in the processing solution of water is from 1 x 10-^s to 1 mol/I.

22. A color photographic print comprising a reflective support having thereon at least one of a layer containing a yellow image-forming dye, a layer containing a magenta image-forming dye and a layer containing a cyan image-forming dye, said photographic print having at least one layer containing at least one compound of (1) and at least one compound of (2) as defined in claim 1.