JPS63123044A - Color image forming method - Google Patents

Abstract

PURPOSE:To improve the aging stability of a photosensitive material, to increase the density of a color image and to reduce fog by developing the photosensitive material contg. a specified developing agent and a slightly water soluble basic metallic compd. with a prescribed processing soln. CONSTITUTION:A photosensitive material contg. photosensitive silver halide, a coupler, a developing agent represented by the formula and a slightly water soluble basic metallic compd. (a) is imagewise exposed and developed with a processing soln. contg. a complex forming compd. (b) which releases a base by a complex forming reaction with a metallic ion in the compd. (a). When zinc hydroxide is used as the compd. (a), sodium picolinate may be used as the compd. (b). In the formula, each of R1-R4 is H, halogen or the like, A is hydroxyl, a group providing hydroxyl by the action of a nucleophilic reagent or the like, R5 is H or F and n=1-17.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color image forming method using a silver halide photosensitive material.

(Prior art and its problems) A general method for forming color images using silver halide photographic light-sensitive materials is to cause a coupling reaction between an oxidized color developing agent and a coupler to form or release a dye. be.

Usually, color developing agents (eg, aromatic primary amine developing agents) are dissolved in aqueous alkaline solutions and used in color developing solutions. If an aromatic primary amine developing agent can be incorporated into a light-sensitive material, development can basically be carried out using only an alkaline aqueous solution. This makes it easier to prepare the developer and reduces changes in the composition of the developer.
Easier to manage. In addition, the BOD of waste liquid is significantly reduced,
There are many advantages such as ease of waste liquid treatment. However, in general, incorporating an aromatic primary amine developing agent into a light-sensitive material causes problems such as sensitization of the light-sensitive material, occurrence of fogging or staining during storage, and insufficient color development due to processing. It has many drawbacks and has not yet been put into practical use.

Black and white developing agents such as hydroquinone and catechol can be incorporated into light-sensitive materials relatively stably. For example, U.S. Patent No. 32.2! , No. 27g shows that it is incorporated as a metal complex salt. On the other hand, aromatic primary amine developing agents are difficult to stably incorporate into light-sensitive materials due to their instability.

Conventionally, several methods are known for incorporating an aromatic primary amine developing agent into a light-sensitive material. For example, US Pat. No. 3,3≠2. In Tatata, Schiff base with salicylaldehyde is used as a developing agent precursor; in US Pat. British Patent No. 1. Ot
In the θ&/ issue, a phthalimide-type precursor is used by reacting an aromatic primary amine with phthalic acid.

Other German patents No. 1. /jri, 73! No. 1.

, 200. No. t7, U.S. Patent No. 3.70! , 0.3
J number etc. are known. However, no matter which technique is used, it is not possible to obtain a solution that satisfies all of the following requirements: sufficient color density, desensitization during storage of the light-sensitive material, and occurrence of fog or stain.

Further, the processing liquid (activator liquid) used in this case must have a high pH value or sufficient development will not occur. Usually, a high alkaline activator solution with a pH higher than 1/2 is used, but the high pH solution has problems such as absorbing carbon dioxide and degrading easily during storage or use, and being dangerous in handling. was there.

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

(Structure of the Invention) The object of the present invention is to form at least a photosensitive silver halide, a coupler, and the following general formula (Z) on a support! - After imagewise exposure, a silver halide photosensitive material containing a basic metal compound that is sparingly soluble in water undergoes a complex-forming reaction with the metal ions constituting the basic metal compound that is sparingly soluble in water to form a base. This is achieved by a color image forming method characterized in that development processing is performed using a processing solution containing a complex-forming compound that releases .

In the formula, R1, R2, R3 and R4 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amine group, a substituted amine group, an acylamino group, an alkylsulfonylamine group,
It represents an arylsulfonylamino group, a substituted carbamoyl group, a carbamoyl group, a substituted sulfamoyl group, a sulfamoyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an acyloxy group, or an alkoxycarbonyl group.

A represents a hydroxyl group, and hydroxyl R7 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a cycloalkyl group, a substituted cycloalkyl group, an aralkyl group, or a substituted aralkyl group due to the action of a nucleophile. )
represents. R5 represents a hydrogen atom or a fluorine atom.

n represents an integer from / to /7. In addition, when R1 to R4 are substituents other than a hydrogen atom, a halogen atom, or a hydroxyl group, they can have further permissible substituents. Further, R1-R4, R6, and R7 may be linked to each other to form a ring consisting of an alicyclic ring, an aromatic ring, a heterocycle, or a combination thereof.

The present invention will be explained in detail below.

R1, R2, R3 and R4 independently represent a hydrogen atom, a halogen atom (preferably chlorine, bromine, fluorine, etc.), a hydroxy group, an amino group, a substituted amine group (for example, as a substituent, the number of carbon atoms is /-/, 2 (preferably /-4 alkyl group, carbon number t to /r aryl group, etc.), acylamino group (preferably carbon 5az-/, 2), alkylsulfonylamino group (preferably carbon/-4), arylsulfonyl Amino group (preferably carbon number &-/2), substituted carbamoyl group (for example, as a substituent, an alkyl group with carbon number /-/2, an aryl group with carbon number 6-/♂, etc.), carbamoyl group, substituted sulfamoyl group C For example, an alkyl group with carbon number/~l as a substituent), an alkyl group (preferably carbon number/-/r), cycloalkyl group C carbon number!
-lO), alkenyl group (carbon number 2 - IO), aryl group f carbon number 6 - lr), aralkyl group (carbon number 7 - lr), aralkyl group (carbon number 7 - lr),
r), alkoxy group (preferably carbon number 7-/J'),
represents an acyl group (preferably carbon number 1-/l), an acyloxy group (preferably carbon number /-/II), or an alkoxycarbonyl group (preferably carbon number 2-/l).

When R1-R4 is a substituent other than a hydrogen atom, a halogen atom, or a hydroxyl group, permissible substituents for R1-R4 (however, substituents, such as halogen atoms, etc., may be present). ) include aliphatic groups, aromatic groups, heterocyclic groups, aliphatic oxy groups, aromatic oxy groups, acyl groups, alkoxycarbonyl groups, carbamoyl groups, imido groups, aliphatic thio groups, aromatic thio groups, and heterocyclic groups. ring thio group,
Aliphatic sulfonyl group, aromatic sulfonyl group, heterocycle
Examples include ter-sulfonyl group, hydroxyl group, cyano group, carboxyl group, sulfo group, and nitro group.

Preferred examples of R1-R4 include a hydrogen atom, a halogen atom, an alkoxy group, an acylamino group, an aryl group, a carbamoyl group, a substituted carbamoyl group, and the like. Further, these may be substituted with a substituent allowed for R1 to R4 above.

A is a hydroxyl group, a group that provides a hydroxyl group by the action of a nucleophilic reagent (for example, an acyloxy group f, e.g., an acetoxy group, a benzoyloxy group, etc.), an alkylsulfonyloxy group (C, for example, a methanesulfonyloxy group), an arylsulfonyloxy group r For example, t is j, a benzenesulfonyloxy group), an alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, etc.), an aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), a dialkylphosphoryloxy group (e.g., (diethylphosphoryloxy group, etc.), diarylphosphoryloxy group (e.g., diphenylphosphoryloxy group, etc.), or substituted alkyl group (preferably carbon number 1~/♂), or substituted alkyl group (preferably 1 carbon number /-it, for example, methanesulfonylaminoethyl group, hydroxyethyl group, etc.), alkenyl group (preferably carbon number λ ~ /2), &-substituted alkenyl group (preferably carbon number λ ~ 7.2), cyclo Alkyl group C preferably number of carbon atoms! ~10), substituted cycloalkyl groups (e.g.
carbon number j~/λ), aralkyl group C, e.g. benzyl group,
β-phenethyl group, etc.), substituted aralkyl group C, e.g. p-chlorobenzyl group, β-(p-chlorophenyl)
(ethyl group, etc.). ). Here, the nucleophilic reagents include 0H-1OR- (R: alkyl group, etc.), 8
Examples thereof include anionic reagents such as 03 and compounds having unshared electron pairs such as l or secondary amines, hydrazines, hydroxylamines, alcohols, and thiols.

Additionally, R1-R4, R6, and R7 are linked to each other to preferably form a j-membered or 6-membered alicyclic ring, aromatic ring, or heterocycle, or a ring consisting of a combination thereof. Good too. For example, preferred examples include a benzene ring in which R1 and R2 or R3 and R4 are connected, a heterocycle in which one or both of R1 and R6, R3 and R7 are connected, and a heterocycle in which R6 and R7 are connected [e.g., pyrrolidino] group, Bi is a lysino group, a morpholino group, etc.).

Preferred examples of A include hydroxyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, dialkylphosphoryloxy group, diarylphosphoryloxy group, dialkylamino group (alkyl group) may be substituted), a pyrrolidino group, a bilydino group, and a morpholino group.

R5 represents a fluorine atom spanning a hydrogen atom. n is /-/
Represents the integer 7.

Preferred specific examples of the developer represented by the general formula [Z]3 are shown below.

α 3゜ r l 3- r r ! .

α α 1/4 - lθ.

α //.

α /2゜ 1/J″- 13+ r Lg.

It.

Ichino 7- -/J- /G.

/7° /L ir- Liri.

2θ.

+21° 2.2゜ 23° Cog.

α C0N(CH312 1/tar +2! .

, 2 Otsu.

I The developing agent used in the present invention can be easily obtained by a known method, that is, by fluoroacylating anilines with a suitable acylating agent.

Specific synthesis examples of the developer used in the present invention are shown below.

Synthesis Example C Synthesis of Exemplary Compound/) Ko, Fuji Chloro≠-Amine Phenol 3! .

11 and acetonitrile souml under ice cooling.
/,01 trifluoroacetic anhydride was added dropwise.

=2 l - After the dropwise addition, the mixture was stirred at room temperature for one hour, and the precipitated crystals were separated by F, and the solvent was distilled off from the ν liquid under reduced pressure. The resulting composition was
-White crystals of exemplified compound/1 by recrystallization from hexane
．． I got 2f. Melting point/z r 'C-,! , 2- The developing agent precursor of the present invention may be used alone or in combination of two or more types. Generally, 0.0. It can be used in a range of 1 to 10 times the mole, preferably 0.2 times to 3 times the mole.

The developer precursor of the present invention can be introduced into the light-sensitive material in many ways. According to a method commonly known as the oil protection method, it may be dissolved in a hydrophobic oil and then emulsified and dispersed in water or in a hydrophilic colloid solution as an oil-in-water droplet dispersion. Alternatively, the compound may be added as fine particles to a hydrophilic colloid solution, or the compound in a solid state may be introduced into water or a hydrophilic binder using a boil mill or the like.

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

Various couplers are known that bind to the oxidized form of a developer. For example, “rhe” by T. H. James S.
theory of tlle photog
4'th Ed, +
334' ~ 3A / page, Makoto Kikuchi - "Photochemistry"
Any of the couplers described in λglI, page 2, etc., published by Kyoritsu Shuppan, can be used in the present invention.

In the present invention, both t-equivalent couplers in which the site that binds to the oxidized form of the developer is a hydrogen atom and di-equivalent couplers in which the site is substituted with a leaving group can be used.

Furthermore, both so-called Fischer dispersion couplers having both a hydrophilic group and a hydrophobic diffusion-resistant group in the coupler and oil-protected dispersion couplers having only a hydrophobic diffusion-resistant group can be used.

Among the couplers having diffusion-resistant groups, there are
Coupler having a hydrophobic ballast group in the leaving group as described in the Oat issue, etc.; JP-A-Sho! Coupler in which a leaving group is linked to the polymer main chain as described in f-/Hirohi, No. 0-7, etc.; U.S. Pat. No. 3,370, No. 52; 3,11. ! /,
1r20 issue; p, oro, r// issue; ≠,, 2/! ,/
Included are polymer couplers described in R.J. Gei.μttn No. 9.320 and the like.

Also, British Patent No. 1.33o, sλhiro;
3ri, /l! No.; Japanese Patent Publication No. 7-/It, No. 7; j7
-KoQ7.2! No. 0; jza-7ri.

Colored couplers containing a dye component in the leaving group, such as those described in No. u+7, are also useful in the present invention.

” Couplers preferably used in the present invention include active methylene and active methine compounds, phenols, naphthols, pyrazoles and fused pyrazole compounds,
Particularly preferred are the following general formulas (■) (■) In the above formula, R8, R9, RIO, R11 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, Aryl group, alkokene group, aryloxy group, acyl group, acylamino group, alkoxyalkyl group, aryloxoalkyl group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, sulfamoyl group, alkylamino group, arylamino group, acyloxy group, It represents a substituent selected from an acyloxyalkyl group, a substituted ureido group, a cyanide group, and a heterocyclic residue. Substituted with sulfo group, cyano group, nitro group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryl group, aryloxy group, aralkyl group, acyl group It's okay if it's done. Xl represents a hydrogen atom or a coupling-off group...a rogene atom, an acyloxy group,
Representative examples of coupling-off groups include sulfonyloxy groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkoxycarbonyloxy groups, dialkylcarbamoyloxy groups, imido groups, N-heterocyclic residues, and pyridinium groups. It is. Great, R8, R9, RIO
, R11 or Xl is preferably a ballast group that provides diffusion resistance, or these groups may be linked to the polymer main chain.

Diffusion-resistant compounds (dye-releasing couplers) that undergo a coupling reaction with an oxidized developer to release a diffusible dye can also be used in the present invention. Compounds of this type include US Pat. -2λ7, jj'0 are representative examples. For example, in the following formula % formula %, Coup represents a coupler residue capable of coupling with the oxidized form of a developer, preferably a portion obtained by removing X from the coupler represented by the above general formula (1) or X). represents.

Link is bonded to the active site of the Coup portion, and when the dye-releasing coupler represented by formula (XI) performs a coupling reaction with the oxidized developer, the bond between the Coup portion and the Coup portion is released. Represents a cleavable group, such as azo group, azoki7 group, -0-1-Hg-, alkylidene group, -5-
In addition to the 1-S-S-1-NH802-1 group, the Campling-Leaving-Kotter-Leaving group X1 described above is also useful.

Dye represents a dye or dye precursor.

Among the dye-releasing couplers represented by the above formula (XI), preferred ones include Coup being a phenolic coupler residue;
Naphthol-type coupler residue or indanone-type coupler residue, pLjnk is an oxygen atom spanning a nitrogen atom, and Co
It connects to up.

Preferably, the dye of formula (XI) is imagewise released and then transferred to the receiver element.

In the present invention, the coupler is U.S. Patent No. 2.322°0.2
It can be introduced into a layer of a photosensitive material by a known method such as the method described in No. 7. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), annzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutquin). High boiling point organic solvents such as ethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), and low boiling point organic solvents with a boiling point of about 3θ0C to /lo 0C, such as ethyl acetate, butyl acetate. lower alkyl acetate,
Ethinope propionate is dissolved in secondary butyl alcohol, methyl imbutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., and then dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Tokko Sho J/-39 and No. 53, Tokko Sho, J/-399
The dispersion method using a polymer described in No. '13 can also be used. Also, when dispersing couplers in hydrophilic colloids,
Various surfactants can be used, and these surfactants are described in JP-A-13-13-636 No. (32).
The surfactants listed on pages 1 to 3 can be used.

The amount of the high-boiling organic solvent used in the present invention is 70 g or less, preferably sg or less, based on the coupler/gK used.

In the present invention, a reducing substance may be used in combination with the photosensitive material. Examples of reducing substances include auxiliary developers that can be used in combination with the developer precursor of the present invention. The auxiliary developer may be diffusible or non-diffusible.

Useful auxiliary developers include hydroquinone, t-butylhydroquinone, 2. These include alkyl-substituted hydroquinones such as odimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, tonoalkoxy-substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N,N-di(-monoethoxy7ethyl)hydroxylamine, /-phenyl-3-virazolidone, goomethyl-gohydroxymethyl-7-phenyl Pyrazolidones such as -3-pyrazolidone, retactones, and hydroxytetronic acids are useful.

Auxiliary developers can be used in a range of concentrations. The useful concentration range is 0゜oooos times molar to 10 times the total amount of coated silver, and particularly effective concentration ranges include θ, θ
0/fold mole to o, is double mole.

In the image forming method of the present invention, a basic metal compound that is sparingly soluble in water is contained in the silver rhodanide photosensitive material, and the basic metal compound that is sparingly soluble in water is contained in the processing liquid. A base is generated in the film of the photosensitive material by containing a compound capable of forming a complex with a metal ion (hereinafter referred to as a complex-forming compound) and performing a complex-forming reaction between the two during processing.

In the present invention, examples of water-refractory basic metal compounds to be included in the light-sensitive material include water solubility (water 700
The number of grams of substance dissolved in g) is preferably expressed by the formula TmXn, where JJ- is θ, 5 or less.

Here, T is a transition metal such as Zn, Ni, Cu, Co,
Alkaline earth metals such as Fe, Mn, etc., such as Ca, Ba,
It represents Mg, etc., and X can serve as a counter ion for M, which will appear in the explanation of complex-forming compounds described later in water,
It also represents something that is alkaline, such as carbonate ion, phosphate ion, silicate ion, borate ion, aluminate ion, hydroxyl ion, and oxygen atom. m and n are
Each represents an integer so that the valences of T and X can be balanced.

Preferred specific examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, calcium magnesium carbonate (CaMg(CO3)2), magnesium oxide, zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, hydroxide Magnesium, calcium hydroxide, antimony hydroxide, -J$- 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 (JZnCO3-3Zn (OH)2 ・H2O), basic magnesium carbonate (3MgcO3 ・Mg(OH)2
・3H20), basic nickel carbonate (N i CO3 ・
Ni (OH) 2 ), basic bismuth carbonate (B
i 2 (CO3) 02・H2O), basic cobalt carbonate (2Co CO3・3Co (OH)2),
Aluminum oxide magne/lum, copper hydroxide, basic copper carbonate, etc.

Among these compounds, colored ones are particularly light and heavy.

In the present invention, the complex-forming compound contained in the treatment liquid forms a complex salt having a stability constant of 7 or more in logK with the metal ion constituting the basic metal compound.

These complex-forming compounds are described, for example, by N.E. Martill and R.M. Smith (A,E).

Martell, R.M., Sm1th), Pakrittical Stability Constance (Crit.
icalStability Con5tants)
, Volumes 1 to 11, Plenum P
ress).

Specifically, aminocarboxylic acids, iminodiacetic acid derivatives, aniline carboxylic acids, pyridine carboxylic acids, amine phosphoric acids, carboxylic acids (mono, di, tri,
Tetracarboxylic acid and compounds having further substituents such as phosphono, hydroxy, oxo, estenopeamide, alkoxy, mercapto, alkylthio, and phosphino), alkali metals such as hydroxamic acids, polyacrylates, and polyphosphoric acids, guanidines, amidines, or 9 Examples include salts such as grade ammonium salts.

Preferred specific examples include picolinic acid, co-pyridinedicarboxylic acid, 2. j-pyridine dicarboxylic acid, cudimethylaminopyridine-21 dicarboxylic acid, quinoline-2-carbo/acid, copyridylacetic acid, oxalic acid,
Citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA.

NTA, CDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, HO2CCH20C
H2CH20CH2CO2H1H02CCH20CH2
Examples include alkali metal salts such as CO2H1 H3 H203P-CH-PO3H2, salts of guanidines, salts of amidines, and guammonium salts.

Among these, aromatic heterocyclic compounds having at least 7 -CO2M groups and 7 nitrogen atoms in the ring are preferred. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -CO2
The position where M is bonded to the ring is particularly preferably α-position with respect to the N atom.

M is any one of an alkali metal, guanidine, amidine and 9th class ammonium ion.

Further examples of lighter and heavier 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 halokene atom, an alkoxy group, -CO2M, a hydroxycarbonyl group, and an electron-donating group such as an amine group, a substituted amine group, and an alkyl group. The two Rs may be the same or different.

zl and Z2 are each the same as the definition in R,
Further, Zl and 22 may be combined to form a ring condensed to the pyridine ring.

Next, the most preferred examples of combinations of slightly water-soluble basic metal compounds and complex-forming compounds are listed (here, M is an alkali metal ion, a substituted or unsubstituted guanidinium ion, an amidinium ion, or a 9-class (represents ammonium ion).

Basic magnesium carbonate - Basic zinc carbonate - Cyclic magnesium carbonate - Calcium carbonate - Zinc oxide - Calcium carbonate - ■Mθ02O20-C02O Calcium carbonate - Barium carbonate - ■MOO2C-CO2eMe Calcium carbonate - M salt of tripolyphosphate Calcium carbonate -MO salt of citric acid-4! /- Calcium carbonate - Magnesium oxide - Zinc hydroxide - H3CCH3 Tin hydroxide - 3CCH3 Magnesium hydroxide - M ■ salt of xametaphosphoric acid Calcium carbonate - Basic magnesium carbonate - ■ M○020. COC02O Calcium carbonate - Basic zinc carbonate - These combinations can be used alone or in combination of two or more.

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

The reaction between the two is shown, for example, by the following formula.

That is, when water in the treatment liquid is involved, picolinate ions cause a complex formation reaction with zinc ions 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 complex formed, but the presence of picolinate ions (Lθ) and zinc ions (M■)
The stability constants of the resulting complexes represented by ML, ML2, and ML3 are very large, as shown below, and explain the progress of this reaction well.

ML ML2 ML3 1og K j , 30 ta, ≦2 /2
．． 9.2 Basic metal compounds that are poorly soluble in water are disclosed in JP-A No. 2-7
7', No. 1130, J3-702733, etc., and the average particle size thereof is preferably less than SOμ, particularly preferably less than jμ.

The basic metal compound in the present invention may be added to any layer such as an emulsion layer, an intermediate layer, a protective layer, an antihalation layer, a white pigment layer, and a back layer. It may be contained in the 7th layer or in 2 or more layers.

The amount added depends on the type of treatment liquid, pH, and complex-forming compound -≠! - It varies depending on the species, compound type of basic metal compound, particle size, processing temperature, etc. - Although it cannot be generally specified, o, o
i~xθg/m2, preferably O1/~,! ;g/
It is best to set it to about 'm2.

The amount of the complex-forming compound added to the processing solution varies depending on the type of processing solution, the type of pH1 complex-forming compound, etc.
It is preferable that the amount is equal to or more than the number of moles of the basic metal compound to be reacted. Generally θ.

It is preferable to set it to about θ/~smol/71.

Although the complex-forming compound is previously contained in the treatment liquid before treatment, it may also be contained in the replenisher liquid.

The silver halide photographic material of the present invention is not only a conventional color photographic material using three types of couplers (yellow, magenta, and cyan), but also a photographic material using a coupler that forms a black image through color development. It can be any material.

The development method for the silver halide photographic light-sensitive material of the present invention may consist of the three steps of development, bleaching, and fixing, and even if bleaching and fixing are carried out at the same time. A method may also be used in which an image is formed from a dye and metallic silver without performing a step (desilvering step). If the dye produced or released is diffusive, it may be diffused into an image receiving element to form an image. In this case, bleaching and fixing steps are not necessary.

The development process used in the present invention differs from conventional development processes in that the development 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 ranges from about 2 to 10, especially from about 7 to 10. A range of l is preferred. The temperature of the activator liquid is selected in the range of: 0C to 200C, but
Preferred is 3θ'C-5o0c.

The activator used in the present invention is basically a common developer (for example, a color developer) from which the developing agent and excess alkaline agent have been removed. Examples of the activator buffer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium or potassium phosphate, potassium metaphosate, borax, etc.
Or used in combination. still provide buffering capacity,
For convenience in dispensing or for the purpose of increasing ionic strength, additionally added sodium or potassium hydrogen phosphate, sodium or potassium λ hydrogen phosphate, sodium or potassium bicarbonate, formic acid, alkali nitrate, alkali sulfate. Various salts can be used.

However, an appropriate amount of anti-fogging agent can also be included.

These include inorganic halide compounds and known organic antifoggants. Representative examples of this inorganic halide compound are bromides such as sodium bromide, potassium bromide or ammonium bromide, and iodides such as potassium iodide or IJium iodide. On the other hand, examples of organic antifoggants include those described in U.S. Pat. No. 2,419T, No. 917θ:
Tropentindazole, US Patent Co., <797.9/
No. 7, and U.S. Patent λ, lj1. , 27/ issue listed!
-Nitropentz imidazo nope Japanese Society of Photography Journal 4 11
Diaminophenazine, 0-phenylenediamine tJj: t:me, mercaptobenzimidazo-/Iz, methylbenzthiazonopemelcabutobenzoxazole, thiouracil, and! -To Methyl Benz Toria Sheets Special Public Show 4#-&/J
Examples include heterocyclic compounds typified by the compound described in No. 75. In addition, the antifoggants described in "Science Photo Handbook" Volume 2, page 779 (Maruzen, published /9!9) can also be used.

For surface layer development control, Japanese Patent Publication No. Shogu G-/9,039, Japanese Patent No. 4T9, US Pat. ．． 29. f.

It is also possible to use development inhibitors known as No. 92 and the like.

In addition, ammonium chloride, potassium chloride, sodium chloride, etc. can be added as necessary. Further, if necessary, any development accelerator can be added in combination. Among these are various pidatarizinium compounds represented by U.S. Pat. Cationic dyes such as thallium nitrate and potassium nitrate, neutral salts such as thallium nitrate and potassium nitrate, US Pat. No. 33,99θ, 2. ．． j3/,?
No. 32, same, 9ta 0, 92θ, same 2, 77th,
/u7 polyethylene glycol and its derivatives,
Nonionic compounds such as polythioethers, Special Publication No. 4
T&-9,309, Belky patent ♂2. The organic solvents described in No. 12, organic amines, ethanolamine, ethylenediamine, jetanolamine, etc. are included. In addition, Photographic Processing Chemistry by L. F. A. Mason
ChemistryJ'70~<73 pages (Focal
Press-London/96≦).

In addition, benzyl alcohol, phenethyl alcohol as described in US Pat. tO- is also an effective development accelerator depending on the purpose.

You can still add sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite.

Furthermore, polyphosphoric acid compounds represented by sodium hexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, or potassium salts of the above-mentioned polyIJ phosphoric acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-(
Aminopolycarboxylic acids such as hydroxymethyl)ethylenediaminetriacetic acid, diethylenetriamine, and tantalic acid can be used as water softeners. The amount added varies depending on the hardness of the water, but is usually θ,j to 10 g.
/ Can be used at around 71. Other calcium,
Magnesium antiseptics can also be used. These are J,
By Wi 11erns [Belgisches Che
miches IndustryJ, 2. /, P3
23 (/9! Otsu) and 23, Pilos (iq
It is detailed in tza).

It can be impregnated with organic solvents if necessary.

These include ethylene glycol, hexylene glycol, diethylene glycol, methyl cellosolve, methanol, ethanol, acetone, triethylene glycol, dimethylformamide, dimethyl sulfoxide,
Others: Tokuko Showa 4t2-33, No. 37, Mawari Goo 9
, No. 309.

The amount added can vary widely depending on the activator component composition, but it is usually the amount of the liquid used! θ% or less, usually 7
It is 0% or less. However, the solvent constituting the activator liquid can sometimes be almost anhydrous.

As an auxiliary developer, N-methyl-p-aminophenol hemisulfate (commonly known as metol), benzyl-p-aminophenol hydrochloride, N,N-diethyl-p-aminephenol hydrochloride, p-aminephenol sulfate, phenide/ , N, N, N'.

N-tetramethyl-p-phenylenediamine hydrochloride and the like can be used. The amount added is usually θ
, θ/~/, Og/l are preferred.

In addition, the following may be added to the activator liquid as necessary.

For example, competitive couplers (colorless couplers) such as citrazic acid, J acid, and H acid include Tokko Shogu'<-9,! 0
No. 3; g4t-□9. j'θ Otsu, rotation -9,,
t07 No., same goo j-/Q, θ36, same 4t goo 9. !
θI No., US Patent, 2 Guko,! No. 32, same 3. ! koθ
, Otsu 9θ, 3. ! Go Ol, No. 272, same 3.1 gj
, No. 737, and the like.

As a fogging agent such as alkali metal polyhydride, aminoborane, and ethylenediamine,
There are things listed in Toto 7 No. Otsu, etc.

The activator treatment of the present invention may be performed in any manner. For example, the photosensitive material is immersed in an activator bath, a well-known hydrophilic polymer as a viscosity imparting agent is added to the activator liquid and this is applied to the photosensitive material, or the activator liquid is placed in a breakable pond and the photosensitive material and image receiving element are separated. There are ways to expand between them.

Conventionally known baths can be used for bleaching, fixing, bleach-fixing and washing or stabilization treatments. Regarding this, for example, see pages 2 to 1 of patent application Sho J/-700jj.
There is a description on page 10.

In addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used as the silver halide used in the light-sensitive material in the present invention. can. The average grain size of the silver halide grains (in the case of spherical or approximately spherical grains, the grain size is taken as the grain diameter, in the case of cubic grains, the principal is taken as the grain size, and expressed as an average based on the projected area) is preferably 2 μ or less, but it is particularly preferred. is 0.4t
It is less than μ. The particle size distribution may be narrow or wide.

The shapes of these silver halide grains are cubic, octahedral,
Any planar shape or mixed crystal shape is acceptable.

Silver halide emulsions are usually prepared by mixing a water-soluble silver salt (for example -!l-silver nitrate) solution and a water-soluble halide salt (for example potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. able to make.

Further, one or more silver halide photographic emulsions formed separately may be mixed. Furthermore, even though the crystal structure of silver halide grains can vary up to the inside, some have a layered structure with different internal and external structures, and some have a different layered structure, as described in British Patent No. 63! , and 9
No. 7, U.S. Patent No. 3. It may also be of a so-called conversion type as described in No. 22.3tF. Further, either a type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the particle may be used.

Two or more types of separately formed silver halogenide emulsions may be mixed and used.

...During the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. are allowed to coexist. Good too.

The soluble salts are usually removed from the emulsion after precipitation or physical ripening.

As the silver halide emulsion, a so-called primitive emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized.

Chemical sensitization methods include sulfur sensitization using active gelatin or compounds containing sulfur that can react with silver ions, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. They can be used alone or in combination.

In order to obtain desired development characteristics, image characteristics, film properties, etc., it may be preferable to further include various additives in the photosensitive material. These additives include iodides in salt form and organic compounds with mercapto free radicals, such as phenylmercaptotetrazole, alkali metal iodide salts, etc.
However, it is desirable to avoid using large amounts of these.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, photosensitive materials may contain, for example, polyalkylene oxide or its ether, derivatives such as estenopeamine, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

For example, in U.S. Pat. No. 3-32, same No. 23. bq number, same number ko, 7/l, 0 otsu- issue, same number 3
．． Go/7, 2e! '0 No. 3,772゜0.27
No. 3. and θ2,0θ3, British Patent No. 1,4tF
, 5', No. 99/, etc. can be used.

Antifoggants are generally added to the photosensitive silver halide emulsion layer and non-photosensitive auxiliary layer of photosensitive materials. Preferred specific examples include heterocyclic organic compounds such as tetrazole, azaindene, and triazole aminopurines. be.

Other additives that may be included in the photosensitive material include hardeners, plasticizers, lubricants, surface agents, brighteners, and other additives known in the photographic art.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

-! 7- For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives, etc. ; Various synthetic hydrophilic polymers such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.; Substances can be used.

In addition to lime-processed gelatin, acid-processed gelatin and pre-treated gelatin (Bull,
Enzyme-treated gelatin as described in Soc, Sci, Phot, Japan) Number (Ban)/l, page 3o (/9 Otsu) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. be able to.

Photographic emulsions can be spectral sensitized, if necessary, by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes and the like.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and cyan, the photosensitive material used in the present invention has at least three layers of halogens that are sensitive to different color regions. It is necessary to have a silver oxide emulsion layer.

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions include 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. A combination of a sensitive emulsion layer and an infrared sensitive emulsion layer, a combination of a blue sensitive emulsion layer, a green sensitive emulsion layer and an infrared sensitive emulsion layer, a blue sensitive emulsion layer, a red sensitive emulsion layer and an infrared sensitive emulsion. There are combinations of layers, etc.

In addition, the infrared light-sensitive emulsion layer is 20θnm or more, especially 7
An emulsion layer that is sensitive to light of gon nm or more.

The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.

In photosensitive materials, it is used as a filter dye in the hydrophilic colloid layer, to prevent irradiation, and for various other purposes.
May contain water-soluble dyes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxynol dyes and merocyanine dyes are useful.

The photosensitive material may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups, goothiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

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

In a photosensitive material, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Photosensitive materials are used as a color fog prevention agent or color mixture prevention agent.
It may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives, and the like.

In the present invention, a known antifading agent can be used in the light-sensitive material or image-receiving element. Examples of organic antifading agents include hydroquinones, 6-hydroxychromans, etc.
Hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminephenols, hindered amines, and the phenolic hydroxyl groups of these compounds. Typical examples include silylated and alkylated ether molybdenum ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Patent No. G, 2tZ, 693,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent the deterioration of magenta dye images, especially the deterioration caused by light, the spiroindanes described in JP-A No. 39-39-9, and the spiroindanes described in JP-A No. 33-9F36, - Chromans substituted with coidoquinone diethers or monoethers give preferable results.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). It may also contain various surfactants for various purposes.

The photographic material may contain an inorganic or organic hardening agent in the photographic emulsion layer and other hydrophilic colloid layers.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde hikodo), N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.)
, dioxane derivative (-!.

3-dihydroxydioxane, etc.), active vinyl compounds (/, 3., !t-1-reacryloyl-hexahydro-8-triazine, /, 3-vinylsulfonyl-2-propanol, etc.), active vinyl compounds compound (,,;:,<
1-dichloro-2-hydroquine-8-triazine)
, mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The photographic material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the 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 (
(e.g. vinyl acetate), acrylonitrile, olefins,
Styrene alone or in combination, or in combination with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. A polymer as a monomer component can be used.

The invention is also applicable to multilayer natural color photographic materials having at least λ different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The present invention is also applicable to color image transfer methods, absorption transfer methods, and the like.

-Bu! Example/A silver halide color photosensitive material was prepared by coating the following first layer (lower layer) to λth layer (upper layer) on a paper support laminated on both sides with polyethylene, and samples/θ/~10 ．． It was set as f.

In addition, samples /θB and /102 were prepared in the same manner except that the second layer of zinc hydroxide was not added
θ2 was also created.

-4A - ■I U In addition, as a gelatin hardening agent for each layer /-oxy-3, j-
Dichloro-8-triazidin sodium salt was used.

After the photosensitive material was imagewise exposed, it was developed according to the following development process.

Activator - 33°C 3 minutes 30 seconds Bleach Fixation 33°C 7 minutes 30 seconds <Activator solution> A B Water FOOml F00
ml Sodium sulfite, Og 2.0g Potassium bromide 0.7g 0.7g Sodium carbonate -2θg Sodium bicarbonate /θg Sodium picolinate 110g - Add water 7000m1J /θ00m1JpH!
, 0 /θ9.2 <Bleach-fix solution> Water e00
ml ammonium thiosulfate (2θ solution) isoml sodium sulfite /J'g ethylenediaminetetraacetic acid iron (1) ammonium jug ethylenediaminetetraacetic acid, 2Na Add water to 1000m100O, 7
0 The results of photographic properties are shown in Table/ below.

-6ter 1N Kaiichi HG3-123044 (19) By treating a photosensitive material containing zinc hydroxide and a developer precursor with an activator solution containing sodium picolinate that forms a complex with zinc ions, a high concentration of A color image of low Capri was obtained.

More photosensitive materials! After aging at θ0C for a week, the same treatment was performed and the minimum concentration was compared with a sample immediately after production.

In samples 10/ and 106, the minimum concentration becomes θ,
y~0. ! In contrast, samples/θ recognition~10j and 107 increased by 0. / or less.

From the above results, it was found that by the method of the present invention, a photosensitive material that is stable over time can be produced, and excellent color images can be obtained using a simple, stable, and safe processing solution.

However, when using activator B whose pH was adjusted to 72 with potassium hydroxide, a maximum concentration of 0.2 degrees and a minimum concentration of 0.2 degrees were obtained for the photosensitive material 102, but this solution was released for several weeks. If left for a while and then processed, the maximum concentration will be /, 2
! It declined to . In contrast, the activator A of the present invention
The same maximum concentration as immediately after preparation was obtained even after leaving the solution for several weeks.

Example/Example/Photosensitive material 10! Photosensitive materials 207 to -O3 having the same structure as photosensitive material 102 were prepared, except that the coupler in the first layer was replaced with the following compound at an equal mole/m2.

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

Photosensitive material Coupler Co θ Co+203 ε Table Core 3- After aging each photosensitive material at 5o0c for a week, we performed similar treatments, and found that the increase in minimum density over time was θ,/ It was below.

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

A well-stirred gelatin aqueous solution (water ioo.

An aqueous solution containing θ, , 29 J-mol of sodium chloride and potassium bromide, respectively, and an aqueous solution of silver nitrate (00 ml of water) containing 20 g of gelatin and 3 g of sodium chloride in mlJ and kept at 7!0C. 0.69 mol of silver nitrate dissolved in the solution) was simultaneously added at an equal flow rate over 90 minutes.

In this way, the average particle size is 0. A <10 μm monodisperse cubic silver chlorobromide emulsion (bromine, 50 molar fraction) was prepared.

After washing with water and desalting, sodium thiosulfate tmg and goohydroxy-O-methyl-/, 3,3EL, ? - θmg of tetrazaindenco was added and chemical sensitization was carried out with gooC. The yield of the emulsion was toog -74'.

Next, I will explain how to make a silver halogenide emulsion for the third layer.

A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 100,100 O of water, 250
(incubated at temperature C) and added sodium chloride and potassium bromide to 0, . 29. An aqueous solution containing t mol
oml and silver nitrate aqueous solution (0.69 silver nitrate in 00ml of water)
(moles dissolved) were simultaneously added at equal flow rates over yo minutes.

In this way, the average particle size θ,3! A monodispersed cubic silver chlorobromide emulsion (bromine gomorch) of μm size was prepared.

After washing with water and desalting, tmg of sodium thiosulfate and θmg of hydroxyl-methyl-/3,3a,7-titrazaindenco were added to carry out chemical sensitization at θ0C. The yield of the emulsion was 6θOg.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

The following yellow dye-providing substance (Y) is tg, succinic acid coethylhexyl ester sulfonic acid sodium o, sg is used as a surfactant, and triisononyl phosphonate is used as a high boiling point organic solvent.

Weigh out 100ml of 100ml of ethyl acetate, add 30ml of ethyl acetate, and make approximately
CK was heated and dissolved to form a uniform solution. This solution and a 70% solution of lime-treated gelatin/θ0g were stirred and mixed, and then dispersed using a homogenizer for 7 minutes at /θ000 rpm. This dispersion is called a yellow dye-providing substance dispersion.

Dispersions of magenta and cyan dye-providing substances were prepared in exactly the same manner as in the preparation of dispersions of yellow dye-providing substances, except that a magenta dye-providing substance (M) and a cyan dye-providing substance (C) were respectively used. .

Using these materials, color photosensitive materials having a multilayer structure as shown in the following table were prepared. 1st and 3rd in the longevity table. Photosensitive materials 3θ/ to 3θg were prepared by changing the developer for the j layer to that shown in Table 3 (common to the 7th, 3rd, and 3rd layers).

Q II ==1 匡　　　2 0 of 1 n (D-2) (D-3) Table-3 Next, we will discuss how to make the dye fixing material.

A dye-fixing material was prepared by coating it on a paper support laminated with polyethylene according to the composition shown in the table below.

-X-1)/, 2-bis(vinylsulfonylacetamido)ethane-1+2) A tungsten light bulb is used in the multilayered color photosensitive material, and a G, R5IR three-color separation filter (G Ha!00~OtsuOOnm, R is OtsuθO~7
00 nm bandpass filter, IR is 20θnm
(constructed using a transmission filter), jθ
Exposure was made for 7 seconds at 0 lux.

20 m 17 m 2 of a 7θ% guanidine picolinate aqueous solution was supplied to the emulsion surface of the exposed light-sensitive material using a wire bar, and then the dye-fixing material and the film surface were superimposed so as to be in contact with each other. When the dye-fixing material is peeled off from the light-sensitive material after sticking for /go seconds using Plenosar, G,
Corresponding to the RlIR three-color separation filter, clear images of yellow, magenta, and -J'/-cyan were obtained. Maximum density of each color (Dma
x) and the minimum density (Dmin) using a Maches reflection densitometer (R
Measured using D-J-/9).

Also, photosensitive materials! After aging at θ0C for a week, the same treatment was performed and the minimum concentration at that time is shown in the table below.

-, r, 2- According to the image forming method of the present invention, a photosensitive material has good stability over time, and a color image with high density and low capri can be obtained.

Patent applicant: Fuji Photo Film Co., Ltd. -r<z-

Claims (1)

[Scope of Claims] A silver halide photosensitive material having on a support at least a photosensitive silver halide, a coupler, a compound represented by the following general formula (Z), and a basic metal compound that is sparingly soluble in water, After image exposure, a color is developed using a processing solution containing a complex-forming compound that causes a complex-forming reaction with metal ions constituting the basic metal compound that is sparingly soluble in water and releases a base. Image forming method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [Z] [In the formula, R_1, R_2, R_3 and R_4 are independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a substituted amino group, an acylamino group, an alkylsulfonylamino group. group, arylsulfonylamino group, substituted carbamoyl group, carbamoyl group, substituted sulfamoyl group, sulfamoyl group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, acyl group, acyloxy group or alkoxycarbonyl group represent. A is a hydroxyl group, a group that gives a hydroxyl group by the action of a nucleophile, or ▲a mathematical formula, a chemical formula, a table, etc.▼(R_6, R_7 are hydrogen atoms, alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, represents a cycloalkyl group, substituted cycloalkyl group, aralkyl group or substituted aralkyl group). R_5 represents a hydrogen atom or a fluorine atom. n represents an integer from 1 to 17. Furthermore, when R_1 to R_4 are substituents other than a hydrogen atom, a halogen atom, or a hydroxyl group, they may have further permissible substituents. Also, R_
1 to R_4, R_6, and R_7 may be linked to each other to form a ring consisting of an alicyclic ring, an aromatic ring, a heterocycle, or a combination thereof. ]