JPH083616B2 - Color image forming method - Google Patents

Description

The present invention relates to a color image forming method using a silver halide light-sensitive material.

(Prior Art and Its Problems) A general method of forming a color image using a silver halide photographic light-sensitive material is a method of forming or releasing a dye by a coupling reaction between an oxidant of a color developing agent and a coupler. .

Usually, a color developing agent (for example, an aromatic primary amine developing agent) is dissolved in an alkaline aqueous solution and used in a color developing solution. When the aromatic primary amine developing agent can be incorporated in the light-sensitive material, the development can basically be carried out only with an aqueous alkali solution. This facilitates the preparation of the developer and eliminates the change in the composition of the developer,
Easy to manage. In addition, the BOD of the waste liquid is remarkably reduced, and the waste liquid can be easily treated. However, in general, incorporating an aromatic primary amine developing agent in a light-sensitive material causes sensitization of the light-sensitive material during storage, generation of fog or stain, and insufficient coloration due to processing. It has many drawbacks and has not yet been put to practical use.

Black-and-white developing agents such as hydroquinone and catechol can be incorporated in the light-sensitive material relatively stably. For example, U.S. Pat. No. 3,295,978 shows that a metal complex salt is incorporated. On the other hand, the aromatic primary amine developing agent is difficult to be stably incorporated in the light-sensitive material because of its instability.

Heretofore, several methods have been known as a method of incorporating an aromatic primary amine developing agent into a light-sensitive material.
For example, U.S. Pat. No. 3,342,599 uses a Schiff base with salicylaldehyde as a developing agent precursor, and U.S. Pat. No. 3,719,492 is used in combination with metal salts such as lead and cadmium. British Patent 1,069,061 uses a phthalimide type precursor by reacting an aromatic primary amine with phthalic acid. Other German patents 1,159,758
No. 1,200,679, and US Pat. No. 3,705,035 are known. However, none of the techniques can provide sufficient color density, desensitization when the light-sensitive material is stored, and generation of fog or stain.

In addition, the processing liquid (activator liquid) used in this case
As a result, sufficient development does not occur unless it has a high pH value. Normally, a high-alkali activator solution with a pH of more than 11 is used. However, such a high-pH solution has problems that it easily deteriorates due to absorption of carbon dioxide during storage or use, and that it is dangerous in handling. .

(Object of the Invention) Accordingly, an object of the present invention is to provide an image forming method capable of forming a high density and high S / N color image in a short processing time by using a photographic material excellent in storage stability and a processing solution. .

(Structure of the Invention) An object of the present invention is to provide a support having at least a photosensitive silver halide, a coupler, a compound represented by the following general formula (Z), and a halogenated compound having a water-insoluble basic metal compound. After the imagewise exposure, the silver light-sensitive material is subjected to development processing using a processing solution containing a complex-forming compound that releases a base by undergoing a complex-forming reaction with the metal ion forming the basic metal compound that is poorly soluble in water. In the color image forming method, the complex-forming compound has at least one —CO ₂ M group (M represents any one of an alkali metal, guanidine, amidine and a quaternary ammonium ion), And a color image forming method characterized by being an aromatic heterocyclic compound having one nitrogen atom in the ring.

[In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, a hydroxyl group, an amino group, a substituted amino group, an alkoxy group. Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, an acyl group, an acyloxy group or an alkoxycarbonyl group, and R ₁ and
R ₂ or R ₃ and R ₄ may combine to form a ring.

A is a hydroxyl group, a group that gives a hydroxyl group by the action of a nucleophile, or (R ₆ and R ₇ represent a hydrogen atom, an unsubstituted or substituted alkyl, alkenyl, cycloalkyl or aralkyl group, and R ₆ and R ₇ may combine to form a heterocycle).

Also, A In the case of, one or both of (R ₁ and R ₆ ) and (R ₃ and R ₇ ) may be linked to form a heterocycle. R ₅ is a cyano group or an alkylsulfonyl group having an unsubstituted or substituted group,
Represents an arylsulfonyl group.

In the general formula [Z], R ₁ , R ₂ , R ₃ and R ₄ are independently
Hydrogen atom, halogen atom (for example, chlorine atom, bromine atom,
Fluorine atom, etc.), alkyl group (preferably alkyl group having 1 to 32 carbon atoms, for example, methyl group, ethyl group, butyl group, octyl group, etc.), alkenyl group (preferably 2 to 32 carbon atoms)
Alkenyl group such as allyl group, vinyl group, crotyl group and the like), cycloalkyl group (preferably cycloalkyl group having 3 to 8 carbon atoms such as cyclohexyl group and cyclopentyl group) and aralkyl group (preferably having 7 to 7 carbon atoms). 18
Aralkyl group such as benzyl group, β-phenethyl group, etc.), hydroxyl group, amino group, substituted amino group, alkoxy group (preferably alkoxy group having 1 to 32 carbon atoms, for example, methoxy group, ethoxy group, benzyloxy group, etc. ) Acylamino group (preferably acylamino group having 2 to 32 carbon atoms, for example, acetylamino group, butyrylamino group, hexanoylamino group, stearoylamino group, etc.) alkylsulfonylamino group (preferably alkylsulfonylamino group having 1 to 32 carbon atoms) For example, methylsulfonylamino group, propylsulfonylamino group, etc., arylsulfonylamino group (preferably arylsulfonylamino group having 6 to 18 carbon atoms, for example, phenylsulfonylamino group,
p-chlorophenylsulfonylamino group etc.), aryl group (eg phenyl group, naphthyl group etc.), carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, acyl group (preferably an acyl group having 2 to 32 carbon atoms, For example, acetyl group, butyroyl group, isobutyroyl group, etc., acyloxy group (preferably having 2 to 32 carbon atoms).
Acyloxy group such as acetyl group, a benzoyloxy group), or an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, represents a methoxycarbonyl group, an ethoxycarbonyl group, etc.), R ₁ and R ₂ Alternatively, R ₃ and R ₄ may combine to form a ring (for example, saturated ring formed by trimethylene group, tetramethylene group, etc., naphthalene ring formed by benzolog, etc.).

When R ₁ , R ₂ , R ₃ or R ₄ is an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group or a group containing an aliphatic hydrocarbon group such as an aralkyl group, an alkoxy group or an acylamino group, these The aliphatic hydrocarbon group may be linear or branched. R ₁ to R ₄ are a hydrogen atom, a halogen atom,
In the case of the substituents other than the hydroxyl group, these are substituents (including a substituent atom) which are permissible for R ₁ to R ₄ described later.
The same applies hereinafter), and when two or more, they may be the same or different.

As the substituents permissible in R ₁ to R ₄ , an aliphatic group,
Aryl group, heterocyclic group, aliphatic oxy group, aromatic oxy group, acyl group, ester group, amide group, imide group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic thio group, arylthio group , Heterocyclic thio group, hydroxyl group, cyano group, carboxyl group,
Examples thereof include a sulfo group and a nitro group.

When R ₁ to R ₄ are a substituted amino group, a substituted carbamoyl group or a substituted sulfamoyl group, the permissible substituents are as described above.
It is synonymous with the permissible substituents for R ₁ to R ₄ .

A is a hydroxyl group, its precursor or In the case of a hydroxyl group precursor, it is a group which gives a hydroxyl group by the action of a nucleophile. Here, as the nucleophile, anionic reagents such as OH ⁻ , OR ⁻ , SO ₃ ²⁻ , primary or secondary amines, hydrazines, hydroxylamines,
Examples thereof include compounds having unshared electron pairs such as alcohols and thiols.

Examples of the hydroxyl group precursor include an acyloxy group (preferably having a carbon number of 1 to 18, such as acetyloxy group, trifluoroacetyloxy group, benzoyloxy group, etc.),
Alkylsulfonyloxy group (preferably having 1 to 1 carbon atoms)
8, for example, methanesulfonyloxy group, etc., arylsulfonyloxy group (preferably having 6 to 18 carbon atoms, for example, phenylsulfonyloxy group, p-chlorophenylsulfonyloxy group, etc.), alkoxycarbonyloxy group (preferably having 2 carbon atoms). ~ 18, for example, a methoxycarbonyloxy group, etc., an aryloxycarbonyloxy group (preferably having a carbon number of 7-18, such as a phenoxycarbonyloxy group, etc.), a dialkylphosphoryloxy group (preferably having a carbon number of 2-12, such as diethyl). Phosphoryloxy group, etc.),
Diarylphosphoryloxy group (preferably having 12 to 12 carbon atoms)
24, such as a diphenylphosphoryloxy group, etc., and the like.

A is In the case of, R ₆ and R ₇ are independently a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having a carbon number of 1 to 32, such as ethyl group, methanesulfonylaminoethyl group, hydroxyethyl group, etc.), substituted or unsubstituted An alkenyl group (preferably having 2 to 18 carbon atoms, such as an allyl group), a substituted or unsubstituted cycloalkyl group (preferably having 3 to 12 carbon atoms, such as a cyclohexyl group), or a substituted or unsubstituted aralkyl group ( Preferably, it has 7 to 18 carbon atoms, for example, benzyl group, β
-Phenethyl group) and R ₆ and R ₇ may be linked to form a heterocycle (eg, pyrrolidine ring, piperidine ring, morpholine ring, etc.). And (R ₁ and R ₆ ) and (R ₃ and
One or both groups of R ₇ ) may be linked to form a heterocycle (eg, tetrahydroquinoline ring, diurolidine ring, etc.).

R ₅ is a cyano group, an unsubstituted or substituted alkylsulfonyl group (preferably having a carbon number of 1 to 18, for example, a methanesulfonyl group, an octylsulfonyl group, etc.), or an unsubstituted or substituted arylsulfonyl group (preferably C6-18, for example, phenylsulfonyl group,
p-chlorophenylsulfonyl group, 2,5-dichlorophenylsulfonyl group, 3,4-dichlorophenylsulfonyl group, 2,4-dibromophenylsulfonyl group, m-nitrophenylsulfonyl group, p-methylphenyl group Sulfonyl group, p-cyanophenylsulfonyl group, α-naphthylsulfonyl group, β-naphthylsulfonyl group, m-methanesulfonylphenylsulfonyl group, p-methoxyphenylsulfonyl group, etc.).

Preferred examples of R ₁ , R ₂ , R ₃ and R ₄ include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an aryl group, a carbamoyl group and a substituted carbamoyl group. Preferred examples of A include a hydroxyl group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a dialkylphosphoryloxy group, a diarylphosphoryloxy group, and a dialkylamino group (wherein the alkyl group is substituted. May be used), pyrrolidino group, piperidino group, morpholino group and the like. Preferred examples of R ₅ include methanesulfonyl group, benzenesulfonyl group, p-chlorophenylsulfonyl group,
Examples include 2,5-dichlorophenylsulfonyl group, m-nitrophenylsulfonyl group, 1-naphthalenesulfonyl group and cyano group.

The preferred specific examples of the developer precursor represented by the general formula [Z] are shown below, but the invention is not limited thereto.

The developer precursor used in the present invention can be synthesized by a known method, for example, an addition reaction of β-substituted ethanols and phenyl isocyanates, or a condensation reaction of β-substituted ethanols and urethanes. it can. The specific synthesis examples of the developer precursor used in the present invention are shown below.

Synthesis Example (Synthesis of Exemplified Compound 1) 15.7 g of phenyl chloroformate was added dropwise to a mixture of 35.6 g of 2,6-dichloro-4-aminophenol and 400 ml of acetonitrile at room temperature.

After stirring at room temperature for 1 hour, the precipitated crystals were separated.
Concentrate the solution under reduced pressure to about half the volume, then add 3N
200 ml of hydrochloric acid was added, and the precipitated crystals were collected and washed with water.

14.9 g of the above crystal was added to β-phenylsulfonylethanol 1
It was mixed with 8.6 g and heated to 130 ° C. under reduced pressure of 10 mmHg. The generated phenol was distilled off, and the mixture was heated and stirred at 130 ° C. for 3 hours. After cooling, 50 ml of ethyl acetate and 50 ml of n-hexane were added, and the formed crystals were collected. The obtained composition was recrystallized from acetonitrile to give 9.2 g of white crystals of Exemplified Compound 1, melting point 179-182 ° C.

The developing agent precursor of the present invention may be used alone or in combination of two or more kinds. Generally, it can be used in a range of 0.1-fold to 10-fold mol, preferably 0.2- to 3-fold mol, based on the total amount of coated silver constituting the photosensitive layer.

The developer precursor of the present invention can be incorporated into the light-sensitive material by many methods. According to a method generally known as an oil protect method, it may be dissolved in a hydrophobic oil to be emulsified and dispersed in water or a hydrophilic colloid solution as an oil-in-water dispersion, or by dissolving in a solvent miscible with water, Alternatively, it may be added as fine particles to the hydrophilic colloid solution, or
The solid state compound may be introduced into water or a hydrophilic binder using a ball mill or the like.

The developer precursor represented by formula (Z) used in the present invention may be added to any layer constituting the color light-sensitive material. Examples thereof include a photosensitive silver halide emulsion layer, a hydrophilic colloid layer, an intermediate layer and the like.

Various types of couplers are known which bond with an oxidized product of a developing agent. For example, “The theory of t” by TH James
Any of the couplers described in "He photographic process", 4th Ed., pp.354-361, Shinichi Kikuchi, "Photochemistry", 4th edition (Kyoritsu Shuppan), pages 284-295, etc. can be used in the present invention.

In the present invention, the site that binds to the oxidized product of the developer is substituted with a 4-equivalent coupler which is a hydrogen atom and a leaving group.
Both equivalent couplers are available. Further, a so-called fisher dispersion type coupler having both a hydrophilic group and a hydrophobic diffusion resistant group in the coupler and an oil protect dispersion type coupler having only a hydrophobic diffusion resistant group can be used. Among couplers having anti-diffusion groups, there is one disclosed in JP
Couplers having a hydrophobic ballast group in the leaving group described in JP-A-58-149,046; couplers in which the leaving group described in JP-A-58-149,047 is linked to a polymer main chain; US Pat.
3,370,952; 3,451,820; 4,080,211; 4,215,195; 4,
The polymer couplers described in No. 409, 320 and the like are included. Further, a colored coupler containing a dye component in the leaving group described in British Patent No. 1,330,524; Japanese Patent Publication No. 48-39,165; JP-A No. 57-186,744; 57-207,250; 58-79,247 and the like is also included in the present invention. Useful for.

The couplers preferably used in the present invention are active methylene and active methine compounds, phenols, naphthols, pyrazoles and condensed pyrazole compounds, and particularly preferable ones are represented by the following general formulas (I) to (X).

In the above formula, R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group,
Aralkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, acyl group, acylamino group, alkoxyalkyl group, aryloxyalkyl group, carbamoyl group, substituted carbamoyl group, sulfamoyl group,
A substituted sulfamoyl group, an alkylamino group, an arylamino group, an acyloxy group, an acyloxyalkyl group, a substituted ureido group, a cyano group, and a substituent selected from a heterocyclic residue, and these substituents are further Alkyl group, alkoxy group, halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, An aryl group,
It may be substituted with an aryloxy group, an aralkyl group or an acyl group. X ¹ represents a hydrogen atom or a coupling-off group, a halogen atom, an acyloxy group, a sulfonyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyloxy group, a dialkylcarbamoyloxy group, an imide group, N-
Heterocyclic residues and pyridinium groups are typical examples of coupling-off groups. Further, any ^one of R ₈ , R ₉ , R ₁₀ , R _{11 and} X ¹ is preferably a ballast group that imparts diffusion resistance, or these groups may be linked to the polymer main chain.

Diffusion resistant compounds (dye releasing couplers) which release a diffusible dye by undergoing a coupling reaction with an oxidized product of a developing agent can also be used in the present invention. Typical examples of this type of compound are the compounds described in US Pat. No. 3,227,550. For example, one represented by the following formula (XI) can be given.

Coup-Link-Dye (XI) In the formula, Coup represents a coupler residue capable of coupling with an oxidized product of a developing agent, preferably a moiety obtained by removing X from the coupler represented by the general formula (I) to (X). Represents

Link is attached to the active site of the Coup part, and
The dye-releasing coupler represented by I) represents a group capable of cleaving the bond between the Coup moiety when the coupling reaction with the oxidation product of the developing agent occurs, and examples thereof include an azo group and an azoxy group.
-O-, -Hg-, alkylidene group, -S-, -SS
-, --NHSO _2- , other groups such as the above-mentioned coupling-off group X
^{1 is} also useful.

 Dye stands for dye or dye precursor.

Among the dye-releasing couplers represented by the above formula (XI), Coup is preferably a phenol-type coupler residue, a naphthol-type coupler residue or an indanone-type coupler residue, and Link is bonded to Coup at an oxygen atom or a nitrogen atom. It is a thing.

The Dye of formula (XI) is preferably transferred to the image receiving element after being imagewise released.

In the present invention, the coupler can be incorporated into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In that case, a high boiling organic solvent such as the following,
A low boiling organic solvent can be used.

For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl). High-boiling organic compounds such as benzoic acid ester (octyl benzoate), alkylamide (eg diethyl laurylamide), fatty acid ester (eg dibutoxyethyl succinate, dioctyl azelate), trimesic acid ester (eg tributyl trimesate) Solvent or low boiling organic solvent having a boiling point of about 30 ° C to 160 ° C, for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone β- ethoxyethyl acetate, methyl cellosolve acetate, then dissolved like cyclohexanone, they are dispersed in a hydrophilic colloid.
The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used. Various surfactants can be used when dispersing the coupler in the hydrophilic colloid, and those surfactants are described in JP-A-59-157636, pages (37) to (38). The agents listed as agents can be used.

The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g or less, relative to 1 g of the coupler used.

In the present invention, a reducing substance may be used in combination in the light-sensitive material. Examples of the reducing substance include auxiliary developing agents that can be used in combination with the developing agent precursor of the present invention. The auxiliary developing agent may be diffusible or non-diffusible.

Useful auxiliary developing agents include hydroquinone, t-butylhydroquinone, alkyl-substituted hydroquinones such as 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and alkoxy such as methoxyhydroquinone. There are polyhydroxybenzene derivatives such as substituted hydroquinones and methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N, N-di- (2-ethoxyethyl) hydroxylamine, 1-phenyl-3-pyrazolidone, 4-methyl-
Pyrazolidones such as 4-hydroxymethyl-1-phenyl-3-pyrazolidone, rectones, and hydroxytetronic acids are useful.

The auxiliary developing agent can be used within a certain concentration range.
A useful concentration range is 0.00005 times mol to 1 of the total coated silver amount.
0 times mole, and particularly useful concentration range is 0.001 times mole to
It is 0.5 times the mole.

In the image forming method of the present invention, the silver halide light-sensitive material contains a water-insoluble basic metal compound, and the processing liquid contains a metal ion forming the water-insoluble basic metal compound. A compound capable of undergoing a complex-forming reaction with a compound having the above structure (hereinafter referred to as a complex-forming compound) is contained, and a complex-forming reaction occurs during processing to generate a base in the film of the photosensitive material. ing.

Examples of the water-insoluble basic metal compound contained in the light-sensitive material in the present invention include solubility in water (100 g of water).
A substance represented by the formula T _m X _n having a gram number of the substance dissolved therein of 0.5 or less is preferable.

Where T is a transition metal, such as Zn, Ni, Cu, Co, Fe, Mn
, Alkaline earth metals, such as Ca, Ba, Mg, etc.,
As X, a counter ion of M, which appears in the description of the complex-forming compound to be described later in water, and exhibits alkalinity, for example, carbonate ion, phosphate ion, silicate ion, borate ion, Represents an aluminate ion, a hydroxy ion, and an oxygen atom. m and n are T and X, respectively.
Represents an integer whose valences can be balanced.

 Preferred specific examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate,
Zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg (Co ₃ ) ₂ ), magnesium oxide, zinc oxide,
Tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide,
Manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, calcium aluminate,
Basic zinc carbonate _{(2ZnCO 3 · 3Zn (OH)} 2 · H 2 O), basic magnesium carbonate _{(3MgCO 3 · Mg (OH)} 2 · 3H 2 O), basic carbonate nickel (NiCO ₃ · 2Ni (OH) ₂ ), basic bismuth carbonate (Bi ₂ (CO ₃ ) O ₂ · H ₂ O), basic cobalt carbonate (2CoCO ₃ · 3
Co (OH) ₂ ), aluminum magnesium oxide, copper hydroxide, basic copper carbonate, etc.

Of these compounds, those that are not colored are particularly preferred.

The complex-forming compound contained in the treatment liquid in the present invention is
It forms a complex salt having a stability constant of 1 or more in log K with a metal ion constituting the basic metal compound.

These complex-forming compounds are described, for example, in AEMartell.RM.
Smith), "Critical Stability Constants", Nos. 1-5
Vol., "Plenum Press.

The complex forming compound of the present invention is an aromatic heterocyclic compound having at least one —CO ₂ M and one nitrogen atom in the ring. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And
The position where —CO ₂ M is bonded to the ring is particularly preferably the α position with respect to the N atom. M is any of alkali metal, guanidine, amidine and quaternary ammonium ions.

More preferred compounds include those represented by the following formula.

formula In the above formula, R represents any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, -CO ₂ M, a hydroxycarbonyl group, and an electron donating group such as an amino group, a substituted amino group, and an alkyl group. . Two Rs may be the same or different.

Z ₁ and Z ₂ are the same as defined in R, and Z ₁ and Z ₂ may combine with each other to form a ring condensed with the pyridine ring.

 Next most preferred basic metal compounds that are hardly soluble in water and their complex forms
Examples of combinations with synthetic compounds are listed (where M Is
Alkali metal ions, substituted or unsubstituted guanidini
Ion, amidinium ion or quaternary ammonium
Um ion).

These combinations may be used alone or in combination of two or more.

Here, the mechanism of generating a base in the film of the photosensitive material in the present invention will be described by taking a combination of potassium picolinate and zinc hydroxide as an example.

 The reaction of both is shown by the following formula, for example.

That is, when water in the treatment liquid is involved, the picolinate ion causes a complex formation reaction with the zinc ion, and the reaction represented by the above formula proceeds, resulting in the generation of a base.

 The progress of this reaction is due to the stability of the resulting complex.
The picolinate ion (L ) And zinc ion
(M ) To generate ML, ML₂, ML₃Of the complex represented by
The stability constant is very large as shown below.
The progress of the reaction is well explained.

Basic metal compounds that are poorly soluble in water are disclosed in JP-A-59-174830,
It is desirable to contain as a fine particle dispersion prepared by the method described in No. 53-102733, etc., the average particle size is
It is preferably 50 μm or less, particularly preferably 5 μm or less.

The addition position of the basic metal compound in the present invention in the light-sensitive material may be any layer such as an emulsion layer, an intermediate layer, a protective layer, an antihalation layer, a white pigment layer and a back layer. Further, it may be contained in one layer or in two or more layers.

The amount to be added varies depending on the type of treatment liquid, pH, complex formation compound species, compound species of basic metal compound, particle size, treatment temperature, etc., and cannot be specified unconditionally, but 0.01 to 20 g / m ² ,
Preferably, it is good to be about 0.1 to 5 g / m ² .

The addition amount of the complex-forming compound contained in the treatment liquid varies depending on the type of treatment liquid, pH, type of complex-forming compound, etc.
It is preferably 1/5 or more of the number of moles of the basic metal compound to be reacted. Generally, it is good to set it to about 0.01 to 5 mol / l.

The complex-forming compound is contained in the treatment liquid before treatment, but may be contained in the replenisher.

The silver halide photographic light-sensitive material of the present invention is not only an ordinary color photographic light-sensitive material using three types of (yellow, magenta, cyan) couplers, but also a photographic light-sensitive material using a coupler that forms a black image by color development. Good.

The development processing method of the silver halide photographic light-sensitive material of the present invention includes a bleaching step (desilvering) regardless of whether it comprises three steps of development, bleaching and fixing. A method of forming an image composed of a dye and metallic silver without performing the step) may be used. If the dye produced or released is diffusive, it may be diffused to an image receiving element to form an image. In this case, the steps of bleaching and fixing are unnecessary.

The developing treatment used in the present invention is different from the conventional developing treatment in that the developing bath is an activator bath containing the complex forming compound, and the other steps can be used as they are.

The pH of the activator is in the range of about 7 to 11, particularly preferably in the range of about 7 to 10.5. The temperature of the activator solution is selected in the range of 20 ° C to 70 ° C, preferably 30 ° C to
50 ° C.

The activator used in the present invention is basically a general developing solution (for example, a color developing solution) from which a developing agent and an extra alkaline agent are removed. As the activator buffer, etc., sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate, sodium or potassium triphosphate, potassium metaphorate, borax and the like are used alone or in combination. Further, for the purpose of giving a buffering capacity, convenience of preparation, or increasing ionic strength, further, sodium phosphate dibasic sodium phosphate, sodium phosphate dibasic sodium phosphate, potassium bicarbonate sodium phosphate, sodium phosphate Various salts such as acids, alkali nitrates and alkali sulfates can be used.

Also, an appropriate amount of antifoggant can be included. These include inorganic halide compounds and known organic antifoggants. Typical examples of this inorganic halide compound are bromides such as sodium bromide, potassium bromide or ammonium bromide, and iodides such as potassium iodide or sodium iodide. On the other hand, examples of organic antifoggants include 6-nitrobenzindazole described in US Pat. No. 2,496,940, US Pat. No. 2,497,917, and US Pat.
5-nitrobenzimidazole described in 6,271, diaminophenazine and o-phenylenediamine described in the Journal of the Photographic Society of Japan, Vol. 11, p. 48 (1948), mercaptobenzimidazole, methylbenzthiazole, mercaptobenz. Examples of the heterocyclic compound include oxazole, thiouracil, 5-methylbenztriazole, and compounds described in JP-B-46-41675. In addition, as the antifoggant, those described in "Science Photographic Handbook", Medium Volume, page 119 (Maruzen, 1959) can be used.

For surface development control, Japanese Patent Publication Nos. 46-19,039 and 45-6,14
It is also possible to use a development inhibitor known in US Pat. No. 9,295,976.

In addition, ammonium chloride, potassium chloride, sodium chloride and the like can be added if necessary. Also,
If desired, any development accelerator can be added together. Among these, U.S. Pat.No. 2,648,604, Japanese Patent Publication No. 44-9,503,
Various pyridinium compounds represented by U.S. Pat.No. 3,671,247 and other cation compounds, cationic dyes such as phenosafuran, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9504, U.S. Pat.
No. 2,531,832, No. 2,950,970, No. 2,577,127, polyethylene glycol and derivatives thereof, nonionic compounds such as polythioethers, JP-B-44-9,509
And organic solvents described in Belgian Patent 682,862, organic amines, ethanolamine, ethylenediamine, diethanolamine and the like. In addition, Photograph Processing Processing Chemistry by LFA Mason "Phot
Graphical Processing Chemistry "40-43 (Focal Pre
ss-London 1966).

In addition, benzyl alcohol, phenethyl alcohol described in US Pat. No. 2,304,925, Journal of the Photographic Society of Japan 14, 74
Pyridine, ammonia, hydrazine and amines described in (1952) are also effective development accelerators for some purposes.

Further, sodium sulfite, potassium sulfite, potassium bisulfate, and sodium bisulfite can be added.

Further, sodium hexametaphosphate, sodium tetrapolyphosphate, sodium polypolyphosphate or polyphosphoric acid compounds represented by potassium salts of the above polyphosphoric acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N- (hydroxymethyl) ) Aminopolycarboxylic acids represented by ethylenediaminetriacetic acid and diethylenetriaminepentacomplex acid can be used as the water softener. Although the amount of addition varies depending on the hardness of the water, it can usually be used at about 0.5 to 10 g / l. Other calcium and magnesium impurities can also be used. These are from Belgisches by J. Willems.
Chemiches Industry "21, P325 (1956) and 23, P110
5 (1958).

 If necessary, organic solvents can be included.

Among them, ethylene glycol, hexylene glycol, diethylene glycol, methyl cellosolve, methanol, ethanol, acetone, triethylene glycol, dimethylformamide, dimethyl sulfoxide, other, JP-B-47-33,378, 44-9,509 described in Compounds are included.

The amount to be added varies widely depending on the composition of the activator, but usually 50% or less of the working solution, usually 10% or less.
% Or less. However, the solvent constituting the activator solution may sometimes be almost anhydrous.

N-methyl-p-aminophenol hemisulfate (commonly called methol), benzyl-p-aminophenol hydrochloride, N, N-diethyl-p-aminophenol hydrochloride, p-aminophenol sulfate, phenidone as an auxiliary developing agent , N, N, N ′, N-tetramethyl-p-phenylenediamine hydrochloride and the like can be used. The amount added is usually preferably 0.01 to 1.0 g / l.

In addition, if necessary, the following substances are added to the activator solution.

For example, as competing couplers (colorless couplers) such as citrazinic acid, J acid and H acid, JP-B-44-9,505,
44-9,506, 44-9,507, 45-14,036, 44
-9,508, U.S. Patents 2,742,832, 3,520,690, and
Examples thereof include those described in Nos. 3,560,212 and 3,645,737.

As a fogging agent such as alkali metal polo hydride, aminoborane, ethylenediamine, etc.
Some are listed in No. 816.

The activator process of the present invention may be performed by any method. For example, a method of immersing a photosensitive material in an activator bath, a method of adding a hydrophilic polymer known as a viscosity-imparting agent to an activator solution, and applying this to a photosensitive material,
For example, the activator solution may be put in a destructible pad and spread between the light-sensitive material and the image-receiving element.

A conventionally known bath can be used for bleaching, fixing, bleach-fixing and washing or stabilizing treatment. This is described, for example, on pages 26 to 40 of Japanese Patent Application No. 61-70055.

As the silver halide used in the light-sensitive material in the present invention, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of the silver halide grains (the grain size is the grain size in the case of spherical or sphere-like grains, the ridge length is the grain size in the case of cubic grains, and is represented by the average based on the projected area) is preferably 2 μ or less, 0.4μ is preferable
It is the following. The particle size distribution may be narrow or wide.

The shape of these silver halide grains is cubic, octahedral,
Any of flat plate and mixed crystal form may be used.

A silver halide emulsion is usually prepared by mixing a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin.

Further, two or more kinds of silver halide photographic emulsions formed separately may be mixed. Further, even though the crystal structure of silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are different, and it is described in British Patent No. 635,841 and U.S. Patent No. 3,622,318. It may be of a so-called conversion type. Further, it may be of a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particles.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together.

Emulsions are usually free of soluble salts after precipitation or physical ripening.

As the silver halide emulsion, a so-called unripened (Primitive) emulsion which does not undergo chemical sensitization can be used.
It is usually chemically sensitized.

For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. Can be used alone or in combination.

It may be preferable that the photosensitive material further contains various additives in order to obtain desired developing characteristics, image characteristics, film physical properties and the like. Examples of these additives include salt-form iodides and organic compounds having a mercapto free radical, such as phenylmercaptotetrazole and alkali metal iodide salts, but it is desirable to avoid using them in large amounts.

For the purpose of increasing the sensitivity, increasing the contrast, or accelerating the development of the light-sensitive material, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt compound, urethane derivative, urea derivative, It may contain an imidazole derivative, 3-pyrazolidones and the like.

For example, U.S. Patent Nos. 2,400,532, 2,423,549, 2,716,062, 3,617,280, and 3,772,021,
Those described in U.S. Pat. No. 3,808,003 and British Patent No. 1,488,991 can be used.

In general, an antifoggant added to the light-sensitive silver halide emulsion layer and the non-light-sensitive auxiliary layer of the light-sensitive material, and preferred specific examples thereof are heterocyclic organic compounds such as tetrazole, azaindene, triazoles aminopurine and the like.

As other additives, the light-sensitive material may contain a curing agent, a plasticizer, a lubricant, a surface agent, a brightening agent and other additives known in the photographic art.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein: hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives: polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
Various synthetic hydrophilic polymer substances such as single or copolymers such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bulletin Society of the Science Phytographie of Japan (Bull.S.
oc.Sci.Phot.Japan) Number (No.) 16,30 pages (1966)
You may use the enzyme-treated gelatin as described in,
Also, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used.

If necessary, the photographic emulsion can be spectrally sensitized by using cyanine dyes such as cyanine, merocyanine and carbocyanine alone or in combination, or by using them in combination with a styryl dye.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan, the light-sensitive material used in the present invention is a silver halide having sensitivity in at least three different spectral regions. It is necessary to have an emulsion layer.

A typical combination of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions is a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. Combination of sensitive emulsion layer and infrared-sensitive emulsion layer, combination of blue-sensitive emulsion layer, green-sensitive emulsion layer and infrared-sensitive emulsion layer, blue-sensitive emulsion layer, red-sensitive emulsion layer and infrared-sensitive emulsion There are combinations of layers. The infrared-sensitive emulsion layer is 700 nm or more, and particularly 740
It means an emulsion layer sensitive to light of nm or more.

The light-sensitive material used in the present invention may optionally have two or more emulsion layers having photosensitivity in the same spectral region depending on the sensitivity of the emulsion.

The light-sensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The light-sensitive material may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

In the light-sensitive material, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based or coumarin-based whitening agent. These may be water-soluble, or a water-insoluble brightener may be used in the form of a dispersion.

In the light-sensitive material, when the hydrophilic colloid layer contains a dye or an ultraviolet absorber, they may be mordanted with a cationic polymer or the like.

The light-sensitive material includes a hydroquinone derivative, an aminophenol derivative, an antifoggant or a color mixture inhibitor.
It may contain amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives and the like.

In the present invention, a known anti-fading agent can be used for the light-sensitive material or the image-receiving element. Organic anti-fading agents include hydroquinones, 6-hydroxychromans, 5
-Hydroxycoumarins, spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the compounds of these compounds Representative examples thereof include ether or ester derivatives obtained by silylating or alkylating a phenolic hydroxyl group. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Compounds having both hindered amine and hindered phenol partial structures in the same molecule as described in U.S. Pat. No. 4,268,593 give good results in preventing the yellow dye image from deteriorating due to heat, humidity and light. Further, in order to prevent deterioration of the magenta dye image, particularly deterioration by light, substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether described in JP-A-55-89835. The chromans given give favorable results.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention, a coating aid, an antistatic agent, an improvement in sliding property,
Various surfactants may be included for various purposes such as emulsion dispersion, prevention of adhesion and improvement of photographic properties (for example, development acceleration, hardening, sensitization).

The light-sensitive material may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy). Dioxane), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halides (2,4-dichloro-6-hydroxy-). s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.), etc. can be used alone or in combination.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or water-soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

The present invention is also applicable to multilayer natural color photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required.
It is usual to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases.

Further, the present invention is applied to a color image transfer method, an absorption transfer method, and the like.

Example 1 A silver halide color light-sensitive material was prepared by coating the following first layer (lower layer) to second layer (upper layer) on a paper support laminated on both sides with polyethylene to prepare samples 101 to 105.

Further, Samples 106 and 107 were also prepared in the same manner as Samples 101 and 102 except that the second layer of zinc hydroxide was not added.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

After the light-sensitive material was imagewise exposed, it was developed according to the following developing process.

<Bleach-fixing solution> Water 400 ml Ammonium thiosulfate (70% solution) 150 ml Sodium sulfite 18 g Ethylenediaminetetraacetic acid iron (I) ammonium 55 g Ethylenediaminetetraacetic acid / 2Na 5 g Water is added 1000 ml pH 6.70 Below are the photographic results. Show.

By processing a light-sensitive material containing zinc hydroxide and a developer precursor with an activator solution containing sodium picolinate complexed with zinc ions, a high density and low fog color image was obtained.

Further, the light-sensitive material was aged at 50 ° C. for 1 week and then subjected to the same treatment, and the minimum density was compared with that of a sample immediately after production. In Samples 101 and 106, the minimum concentration increased with time by 0.4 to 0.5, while in Samples 102 to 105 and 107, it was 0.1 or less.

From the above results, it was found that the method of the present invention can produce a photosensitive material which is stable over time and can obtain an excellent color image using a simple, stable and safe processing solution.

Also, when the pH of activator B was adjusted to 12 with potassium hydroxide, the maximum concentration of 1.85 and the minimum concentration of 0.25 were obtained for the light-sensitive material 102, but when this solution was left open for 4 weeks, it was processed. The maximum concentration dropped to 1.25. On the other hand, with the activator A of the present invention, the maximum concentration was obtained even after standing for 4 weeks, which was similar to that immediately after the preparation.

Example 2 A light-sensitive material 10 except that the coupler of the first layer was replaced by the following compound in an equimolar amount / m ^{2 in} the light-sensitive material 105 of Example 1.
Photosensitive materials 201 to 203 having the same structure as in No. 2 were prepared.

When the same treatment was carried out using the activator A solution of Example 1, the results shown in Table 2 were obtained.

When each photosensitive material was aged at 50 ° C. for 1 week and then subjected to the same processing, the minimum density increase with time was 0.1 or less in all cases.

Example 3 A method for preparing a silver halide emulsion for the first and fifth layers will be described.

0.295 each of sodium chloride and potassium bromide in a well-mixed gelatin aqueous solution (containing 1000 g of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C).
600 ml of mol-containing aqueous solution and silver nitrate aqueous solution (water 600 m
(1) in which 0.59 mol of silver nitrate was dissolved) was simultaneously added at an equal flow rate over 40 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.40 μm (bromine
50 mol%) was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was performed at 60 ° C. Emulsion yield is 60
It was 0g.

Next, how to prepare a silver halide emulsion for the third layer will be described.

0.295 each of sodium chloride and potassium bromide in a well-mixed gelatin aqueous solution (containing 1000 g of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C).
600 ml of an aqueous solution containing moles and an aqueous solution of silver nitrate (600 ml of water
0.59 mol of silver nitrate) was added simultaneously over 40 minutes at an equal flow rate. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was performed at 60 ° C. Emulsion yield is 60
It was 0g.

Next, a method for preparing a gelatin dispersion of a dye-donor substance will be described.

5 g of the following yellow dye-donating substance (Y), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 2.5 g of triisononyl phosphonate as a high-boiling organic solvent were weighed, and acetic acid was added. 30 ml of ethyl was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution and 100 g of a 10% solution of lime-processed gelatin were mixed by stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes.
This dispersion is referred to as a yellow dye-donor substance dispersion.

Dispersions of magenta and cyan dye-donor substances were prepared in exactly the same manner as the dispersion of yellow dye-donor substances except that magenta dye-donor substance (M) and cyan dye-donor substance (C) were used. .

From these, a multi-layered color light-sensitive material as shown in the following table was produced. Note that the developing agents for the 1st, 3rd, and 5th layers in the table are replaced with those shown in Table 3 (common to the 1st, 3rd, and 5th layers).
Created 6.

Next, how to make the dye fixing material will be described.

A dye fixing material was prepared by coating on a paper support laminated with polyethylene in the constitution shown in the following table.

A tungsten light bulb is used for the above-mentioned multi-layered color light-sensitive material, and G, R, and IR three-color separation filters whose densities are continuously changed (G is 500 to 600 nm, R is 600 to 700 nm bandpass filter, IR is Exposure was carried out for 1 second at 500 lux through a filter having a transmission of 700 nm or more).

20 ml / m ² of a 10% guanidine picolinate aqueous solution was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then the dye-fixing material and the film surface were superposed. When the dye fixing material was peeled from the light-sensitive material after being adhered for 150 seconds using a presser, a clear image of yellow, magenta and cyan was obtained on the fixing material corresponding to the three color separation filters of G, R and IR. It was The maximum density (Dmax) and the minimum density (Dmin) of each color were measured using a Macbeth reflection densitometer (RD-519).

The light-sensitive material was aged at 50 ° C. for 1 week and then processed in the same manner, and the minimum density at that time is shown in the following table.

According to the image forming method of the present invention, it is possible to obtain a color image of a light-sensitive material having good stability over time and having high density and low fog.

Claims (1)

[Claims] 1. A silver halide light-sensitive material having at least a light-sensitive silver halide, a coupler, a compound represented by the following general formula (Z) and a water-insoluble basic metal compound on a support is imaged. After exposure, a color image is developed by using a processing solution containing a complex-forming compound that undergoes a complex-forming reaction with the metal ion constituting the water-insoluble basic metal compound to release a base. In the forming method,
As the complex-forming compound, a —CO ₂ M group (M is an alkali metal,
A color image forming method comprising an aromatic heterocyclic compound having at least one of guanidine, amidine and a quaternary ammonium ion) and having one nitrogen atom in the ring. . [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, a hydroxyl group, an amino group, a substituted amino group, an alkoxy group. Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, an acyl group, an acyloxy group or an alkoxycarbonyl group, and R ₁ and R ₂
Alternatively, R ₃ and R ₄ may combine to form a ring. A is a hydroxyl group, a group that gives a hydroxyl group by the action of a nucleophile, or (R ₆ and R ₇ represent a hydrogen atom, an unsubstituted or substituted alkyl, alkenyl, cycloalkyl or aralkyl group, and R ₆ and R ₇ may combine to form a heterocycle). Also, A In the case of, one or both of (R ₁ and R ₆ ) and (R ₃ and R ₇ ) may be linked to form a heterocycle. R ₅ represents a cyano group or an unsubstituted or substituted alkylsulfonyl group or arylsulfonyl group. ]