JPS63271445A - Image forming method - Google Patents

Abstract

PURPOSE:To ensure aging stability and safety for a developing soln. by using a photosensitive material contg. a specified compd. CONSTITUTION:A silver halide photosensitive material holding a photosensitive silver halide emulsion, a compd. represented by the formula and a slightly water soluble basic metallic compd. on the support is developed with a processing soln. contg. a compd. which causes a complex forming reaction with the metal ion in the metallic compd. and releases a base. Thus, aging stability and safety can be ensured for the developing soln. In the formula, PWR is a group which releases (Time)tPUG by reduction, Time is a group which releases PUG through a reaction subsequent to the reduction after release as (Time)tPUG from PWR, t=0 or 1 and PUG is a photographically useful group.

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to an image forming method using a silver halide photosensitive material.

PRIOR ART AND PROBLEMS THEREOF Provides photographically useful compounds that incorporate photographic reagents in photographic elements that are immobile in nature, or are ballast stabilized, or are blocked at active sites. The compounds described in Belgian Patent No. 810,195, U.S. Pat.
80.479, U.S. Pat. No. 4,139,379, and Japanese Patent Application Laid-Open No. 130927/1983, the positive-forming compounds are included. Such compounds are immobile or photographically inert, but are capable of undergoing intramolecular nucleophilic substitution or intramolecular electron transfer reactions to release a mobile, photographically useful group. I can do it.

Although the compounds having the functions just described each have many advantages, many of them can function satisfactorily under normal processing conditions for silver halide photosensitive materials, but many of them have higher Requires pH and higher processing temperatures. Therefore,
There was a drawback that the stability and safety over time of the processing solution used, especially the developer solution, could not be sufficiently ensured.

■ Purpose of the Invention The purpose of the present invention is to provide an image forming method that can ensure stability and safety over time of a processing solution, especially a developer, and can obtain a high pH when necessary, resulting in an image forming method with excellent photographic properties. It is about providing.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, the present invention provides a silver halide photosensitive material having a photosensitive silver halide emulsion, a compound represented by the following general formula (I), and a basic metal compound that is sparingly soluble in water on a support. This image forming method is characterized by developing with a processing solution containing a compound that causes a complex formation reaction with metal ions constituting a soluble basic metal compound and releases a base.

General formula (I) PWR+T i me+1 PUG (In the above general formula (I), PWR represents a group that releases -(Time)-tPUG by being concentrated, and Time represents +T i me+tIiUG from PWR.
represents a group that releases PUG through a subsequent reaction after being released as PUG. t represents O or 1, PUG
represents a photographically useful group. ) ■Specific structure of the invention The specific structure of the present invention will be explained in detail below.

In the image forming method of the present invention, a 1:A basic metal compound that is sparingly soluble in water is contained in the silver halide photosensitive material 1, and the above-mentioned 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 (hereinafter referred to as a complex-forming compound) that can undergo a complex-forming reaction with the metal ions constituting the photosensitive material, and the two perform a complex-forming reaction during processing.

In the present invention, examples of basic metal compounds that are sparingly soluble in water and contained in the light-sensitive material include water solubility (water 1 o
It is preferable that the durham a) of the substance dissolved in og is 0.5 or less and is represented by the formula TJn xn.

Here, T is a transition metal, such as Zn or Ni.

Cu%C01Fe%Mn, etc., represents an alkaline earth metal such as Ca, Ba, 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 represent integers such that the valences of T and X are balanced, respectively.

Preferred specific examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate ((:aMg((:03) 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 (Slr+tl:0
．． -3Zn(Oil)2-t120), basic magnesium carbonate (:1Mg11:03・Mg(01ri2・3+
120), basic nickel carbonate (Ni(:(h・2N
i (OH)2 ), basic bismuth carbonate (Bi2(
COa)02 ・1120), basic cobalt carbonate (2
(:o(:03 ・3Co(011) 2 ), aluminum magnesium oxide, copper hydroxide, basic copper carbonate, etc.

Among these compounds, uncolored compounds are particularly preferred.

In the present invention, the complex-forming compound contained in the treatment liquid forms a complex salt having a stability constant of 1 or more in logarithm with the metal ion constituting the basic metal compound.

These complex-forming compounds are described, for example, by N.E. Martyr, R.M. Smith (A, [i, Mar
Lell, R, M, Sm1th), “Critical Stability Constance” ((:riticalS
"Tability Con5tants", Volumes 1-5, Plenua+ Press.

Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, aniline carboxylic acids, pyridine carboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri,
Tetracarboxylic acids and compounds with substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), alkali metals such as hydroxamic acids, polyacrylates, and polyphosphoric acids, guanidines, and amidines. Alternatively, salts such as quaternary ammonium salts may be mentioned.

Preferred specific examples include picolinic acid, 2.6-pyridinedicarboxylic acid, 2.5- and lysinedicarboxylic acid, 4.
-dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid, oxalic acid, citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA% NTA, CDTA% hexametaphosphoric acid, Tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, 1102 (:C1l 20GII 2 [1120[
:ll2C02It.

1102 CC112 (Ll: 112 CO2H.

Examples include alkali metal salts such as guanidine salts, amidine salts, and quaternary ammonium salts.

Among these, aromatic heterocyclic compounds having at least one -CO2M and one nitrogen atom 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 -C
The position where O2M 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 quaternary ammonium ion.

More preferable 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, -CO2M, a hydroxycarbonyl group, and an electron-donating group such as an amino group, a substituted amino group, and an alkyl group. Two R's may be the same or different.

Zl and 22 are each the same as defined 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 quaternary (represents ammonium ion).

Basic magnesium carbonate - Basic zinc carbonate - Basic magnesium carbonate - Calcium carbonate - Zinc oxide - ee ee Calcium carbonate - MO2C-C02M Calcium carbonate - ee ee Barium carbonate - M 02 C-CO2M Calcium carbonate - Magnesium oxide - Hydroxide Zinc - Tin hydroxide - II 3 (: C113 Magnesium hydroxide - M of hexametaphosphoric acid Calcium carbonate - Basic magnesium carbonate - Calcium carbonate - Basic zinc carbonate - These combinations can be used alone or in combinations of two or more. It can also be used in combination with h.

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.

In other words, when water in the treatment liquid is involved, picolinate ions! (2) A complex formation reaction occurs with lead 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 progress of this reaction is due to the stability of the complex formed, and
ML generated from ML2. The stability constant of the complex represented by ML3 is very large as shown below and explains the progress of this reaction well.

M L M L 2 M L :5
11ozK 5.30 9.62 12.
92 basic metal compounds are disclosed in JP-A-59-174830;
It is desirable to contain it in the form of a fine particle dispersion prepared by the method described in Japanese Patent No. 53-102733, and the average particle size thereof is preferably 50 μm or less, particularly 5 μm or less.

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. Moreover, it may be contained in one layer or in two or more layers.

The amount added varies depending on the type of complex-forming compound, basic metal compound type, particle size, processing temperature, etc., or depending on the processing method such as immersion processing or coating processing, but the important thing is that the pH in the photosensitive layer is The amount may be sufficient as long as it becomes sufficiently alkaline, and is generally about 0.01 to 20 g/m2, preferably about 0.1 to 5 g/m2.

The amount of the complex-forming compound added to the developer varies depending on the method of applying the developer to the photosensitive material, the pH of the developer, the type of complex-forming compound, etc. It is preferable to set it as 10 or more. Generally 0
．． It is preferable to set it to about 01 to 10o+ol/42.

In the present invention, the above-mentioned complex-forming compound is added to the processing solution, and the photosensitive material is brought into contact with this processing solution to cause the basic metal compound and the complex-forming compound to react, and the pH in the coating film is
to rise.

The amount of the complex-forming compound added to the processing solution varies depending on the method of applying the processing solution to the photosensitive material, the pH of the processing solution, the type of complex-forming compound, etc., but it should be at least 1/10 of the number of moles of the basic metal compound to be reacted. It is preferable that Generally 0.01~
It is preferable to set it to 10 mol/It.

This processing liquid may be a developer, or a liquid applied before or after it. This treatment liquid allows the compound of general formula (1) of the present invention to function (PUG
or release Time-PUG) v:! A or previously applied to the photosensitive material of the present invention.

There are no restrictions on the method of applying the processing solution of the present invention to the photosensitive material, and the most commonly used method is to immerse the photosensitive material in a processing solution tank (immersion processing), or to apply the processing solution to the photosensitive material and the web sheet. A method of spreading the processing liquid into the gap (development processing), a method of spraying the processing liquid onto the film surface of the photosensitive material (spraying processing or spraying is a process, the details of which are described in JP-A-61-80150), a method of spraying the processing liquid onto the film surface of the photosensitive material A method in which the processing liquid acts on a laminar liquid film (laminar flow thin layer processing), a method in which the processing liquid is applied to the photosensitive material and it acts in the form of a liquid film (application is a thin layer process, details of which can be found in JP-A No. 6)
1-80149) can be applied.

Among these, the thin film processing method is suitable for coating. The coating process of the thin film treatment method includes roller coating, dip coating, slide hopper coating, hopper coating, kiss coating, and a method of applying a solution impregnated in a material that absorbs the processing solution, such as felt cloth or a sponge sheet. Any known method can be used.

For details, please refer to "Coating Science" by Yuji Harasaki (especially 2253-255), Asakura Shoten (1971), "Paper Processing Handbook" edited by Shigyo Times, P129-138 (1978).
), etc., and specifically the following methods are listed.

(1) air doctor coater (2) blade coater (1) lade coater (3) rod coater (4) knife coater (5) squeeze coater ( 6)
impregnation coater
er) ()) Reverse roll coater (8) Transfer roll coater (9)
gravure coater
(lO) Kiss roll coater (11) Cast coater (12) Spray coater (13)
) Curtain coater'
)(14) Calendar coater
coater) (15) Extrusion coater (extrus
ion coater) The viscosity of the treatment liquid is appropriately adjusted depending on the desired coating liquid thickness and application method. Although there may be no need to increase the viscosity, in some cases it is preferable to add some thickener (for example, carboxymethylcellulose).

In this case the viscosity is between 1 and 10 centipoise at 20°C, more preferably between 1 and 5 centipoise.

No matter which method is used, the total liquid film thickness (including the swelling part of the film) is preferably 1000 μm or less, more preferably 50 to 500 μm, and even if it is less than 10 μm.
It is necessary to have a thickness of μm or more.

If the thickness exceeds 300 μm, it will be impossible to coat the photosensitive material as a liquid film unless the viscosity increases, and if the thickness is around 300 μm, coating is possible, but it will be difficult to leave the liquid still on the surface of the photosensitive material. On the other hand, if the thickness is less than 10 μm, it becomes difficult to apply the coating uniformly.

Laminar flow thin layer processing is also one of the preferred application methods of the present invention.
This method will be explained in detail below, but
It is detailed in No. 77851. The degree of laminar flow state is better as the flow of the liquid on the surface of the photosensitive material is smaller, and a Reynolds number of 2,000 or less is desirable, and a Reynolds number of 500 or less is particularly convenient.

The Reynolds number Re is the effective thickness of the liquid layer D, the velocity V,
If the density is ρ and the viscosity is μ, it is given by DVρ/μ.

Here, the effective thickness D is the distance between the photosensitive material surface and the container wall surface;
Alternatively, it refers to the thickness between liquid chambers, such as between surfaces of photosensitive materials. In addition, the speed V is considered to be the relative speed of the processing liquid to the photosensitive material, but as the effective thickness D of the liquid layer becomes smaller, the relative speed between the processing liquid and the vessel wall also affects the actual ha. It is used as the average V of the two relative velocities.

As long as the Reynolds number does not exceed a critical value, the liquid flow remains laminar.

In the present invention, the effective thickness D of the liquid layer is about 0.5 to 10 mm, and the density ρ is almost the same as the density of water since it is an alkaline aqueous solution, and is about 1.0 to 1.1 at room temperature. Further, the viscosity μ is 0.9 to 2 centipoise at 20°C.

The viscosity increases when a thickener is used, which expands the flow rate range in which laminar flow can be maintained.However, the advantage of bath development intensification processing is that it is difficult to remove the adhered liquid after processing. Samples with thickeners are not preferred because new problems such as

The velocity V is calculated from the Reynolds number Re to maintain laminar flow, and theoretically it is up to 2 m/s if the effective thickness D of the liquid layer is 0.5 mm, and 0 if D is 10 mm.
It is possible to increase the speed up to 1 m/s. However, in reality, if the speed V is large, slight irregularities on the sample or vessel wall will easily disturb the liquid, so the smaller the speed V is, the safer it is, and even if the effective thickness D of the liquid layer is small, it is 0.1 m/ s or less, and more preferably about 10-'' to 10-' m/s.

There are various embodiments that implement laminar flow conditions.

For example, there is a method in which a liquid film is formed on a ring surrounded by the circumferential surfaces of two concentric drums, and a photosensitive material on a roll is immersed into the liquid film along the circumferential surface.

This can be achieved by fixing the photosensitive material on a drum and rapidly feeding the processing solution, and then using the batch processing method, in which the solution is also stationary, or by feeding the photosensitive material and the processing solution from one side of the drum to maintain a sufficient relative speed between the two. There is a continuous processing method in which the photosensitive material is taken out from the other end of the drum at a slower rate and the used processing solution also overflows.

In the latter case, a co-current type feed system gives much better results than a counter-current type. This is not only because the Reynolds number can be kept small, but also because it is significant that the liquid that comes into contact with the photosensitive material at the beginning is not a used liquid, but a fresh liquid that is fed at the same time. .

Next, the compound represented by general formula (I) used in the present invention will be explained.

General formula (I) PWR(-T i me-)-1PUG General formula (I)
), PWR represents a group that releases (Time-)IPUG upon reduction.

Time represents a group that is released from PWR as (Time+1-PUG) and then releases PUG through a subsequent reaction.

t represents an integer of 0 or r.

PUG represents a group which becomes a photographically useful group after being released.

First, PWR will be explained in detail.

PWR is based on U.S. Pat. No. 4,139,389 or U.S. Pat. No. 4,139,379, U.S. Pat.
No., JP-A-59-185333, JP-A No. 57-84453
Even if it corresponds to a moiety containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in No. Good, U.S. Patent No. 4,232,1
No. 07, JP-A-59-101649, Research Disclosure (1984) rV, 24025, or JP-A-61-88257, photographic reagents that undergo intramolecular electron transfer reaction after being reduced. It may correspond to a moiety containing an electron-accepting quinonoid center and a carbon atom that connects it to a photographic reagent in a compound that is eliminated. Also, JP-A-56
-142530, U.S. Patent No. 4,343,893,
An aryl group substituted with an electron-withdrawing group in a compound whose single bond is cleaved to release a photographic reagent after reduction as disclosed in U.S. Pat. No. 4,619,884 and the atom linking it to the photographic reagent. (a sulfur atom, a carbon atom, or a nitrogen atom). It also corresponds to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom that connects it to the photographic reagent, as disclosed in U.S. Pat. No. 4,450,223. It's okay to have,
Corresponds to the geminal dinitro moiety in the dinitro compound that β-eliminates the photographic reagent after electron acceptance and the carbon atom-containing moiety that links it to the photographic reagent described in U.S. Pat. No. 4,609,610. It may be. However, in order to more fully achieve the object (1) of the present invention, among the compounds of general formula (I), those represented by general formula (II) are preferred.

General formula (II) E A G-- In the above general formula (II), ■EAG (Time+1-PUG is bonded to at least one of R1%R2 or EAG.

The portion corresponding to pwk in general formula (II) will be explained.

X is oxygen atom (-0-), sulfur atom Was.

R1, R2 and R3 represent groups other than hydrogen atoms or simple bonds.

Groups other than hydrogen atoms represented by R1, R2S and R3 are listed below.

M or - Gastric alkyl group Methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethylno^, ethoxycarbonylmethyl group, aminomethyl group, acetylaminomethyl group, ethyl group, 2-(4- dodecanoylaminophenyl) ethyl group, carboxyethyl group, allyl group, 3,3゜3-trichloropropyl group, n-propyl group, 1so-
Propyl group, n-butyl group, 1so-butyl group, 5ec
-Butyl group, t-butyl group, n-pentyl group J4.5
ec-pentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, 5ec-hexyl group, t-hexyl group, cyclohexyl group, n-octyl group, 5ec-octyl group, t-butyl group, n- Decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, 5ec-hexadecyl group, t-hexadecyl group, n-octadecyl group, t
-octadecyl group, etc.

7. Alkenyl J vinyl group, 2-chlorovinyl group, 1-methylvinyl group,
2-cyanovinyl group, cyclohexen-1-yl group, etc.

1 negative or -1 alkynyl group, ethynyl group, 1-propynyl group, 2-ethoxycarbonylethynyl group, etc.

If the aryl group of ′ξ is phenyl group, naphthyl group, 3-hydroxyphenyl group,
3-chlorophenyl group, 4-acetylaminophenyl group, 4-hexadecanesulfonylaminophenyl group, 2-
methanesulfony) Lt-4-nitrophenyl group, 3-
Nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, 4-tetradecyloxyphenyl group, etc. 'Xi or ~ bitterness
-2r group 1-imidazolyl group, 2-furyl group, 2-pyridyl group,
5-nitro-2-pyridyl group, 3-pyridyl group, 3.5
-dicyano-2-pyridyl group, 5-tetrazolyl group, 5
-phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2-benzimidazolyl group, 2-benzoxasilyl group, 2-xacillin-2-yl group, morpholino group, etc.

Wt acyl 1-acetyl group, propionyl group, butyroyl group, 1so-
butyroyl group, 2,2-dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group, 3-acetylamino-4-methoxybenzoyl group, 4-methylbenzoyl group, 4-methoxy-3-sulfobenzoyl group, etc.

Alternatively; carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis-(2-methoxyethyl)carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, di-
n-octylcarbamoyl group, 3-dodecylpropylcarbamoyl group, hexadecylcarbamoyl group, 3-(
2,4-di-t-pentylphenoxy)propylcarbamoyl group, 3-octanesulfonylaminophenylcarbamoyl group, di-n-octadecylcarbamoyl group, etc.

Sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, diethylsulfamoyl group, bis-
(2-methoxyethyl)sulfamoyl group, di-n-butylsulfamoyl group, methyl-n-octylsulfamoyl group, n-hexadecylmethylsulfamoyl group,
3-ethoxypropylmethylsulfamoyl group, N-phenyl-N-methylsulfamoyl group, 4-decyloxyphenylsulfamoyl group, methyloctadecylsulfamoyl group, etc.

Methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, butanesulfonyl 3% n-octanesulfonyl group, n-dodecanesulfonyl group, n-hexadecanesulfonyl group, benzenesulfonyl group, 4-toluenesulfonyl group, 4- n-dodecyloxybenzenesulfonyl group, etc.

R1 and R3 are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic residues, acyl groups, sulfonyl groups, and the like. The number of carbon atoms in R1 and R3 is preferably 1 to 40.

R2 is preferably a substituted or unsubstituted acyl group or sulfonyl group. The number of carbon atoms is preferably 1 to 40.

R1, R2, R3 and EAG are bonded to each other to form 5-8
A ring of members may be formed.

EAG will be described later.

Furthermore, in order to achieve the object of the present invention, general formula (II)
Among the compounds represented by formula (III), those represented by general formula (III) are preferred.

General formula (III) In the above general formula (I[I), EAG corresponds to the PWR shown in general formula (1).

(Time+1-PUG binds to at least one of R4 and EAG.

The portion corresponding to PWR in general formula (III) will be explained.

Circle Y is a divalent linking group, preferably -C- or -5
It is 02-. X has the same meaning as above.

R4 represents an atomic group that combines with X and Y to form a 5- to 8-membered monocyclic or condensed heterocycle including a nitrogen atom.

Preferred examples of the portion corresponding to this heterocycle are listed below.

Here, R8, )t9 and RIG are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or the like. R” represents an alkyl group, an aryl group, an acyl group, or a sulfonyl group. (Time −) EPLJG&;tRa,
R9, R"j: Good binding.

EGA represents an aromatic group that accepts or takes electrons from a reducing substance and is bonded to a nitrogen atom. As EGA, a group represented by the following general formula [A] is preferable.

General formula (A) ε In the above general formula (8), represents.

Vn represents an atomic group forming a three- to six-membered aromatic group together with zl and z2, and n represents an integer from 3 to 3.

V3 knee 23-1V4;-23-24-1V5;
-z3-z4-z5-1v6;, z3-24-z,,
-za-1V7 knee 23-24-Zs -za -
27-1Va ;-z3-z4-25-26 27-
Zg -. Kokote, -0-1-S-1 or -5o2-, Sub represents a simple combination (
π bond), a hydrogen atom, or a substituent described below. 'Sub may be the same or different, or may be bonded to each other to form a 3- to 6-membered saturated or unsaturated carbocyclic or heterocyclic ring.

In general formula (A), Sub
Select.

EAG will be described in more detail.

EAG represents a group that accepts and takes electrons from reducing substances,
Bonds to nitrogen atoms. EAG is preferably an aryl group or a heterocyclic group substituted with at least one electron-withdrawing group. Substituents bonded to the aryl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire compound. Examples of the overall physical properties of the compound' include, in addition to adjusting the ease with which it accepts electrons, it also has water solubility, oil solubility, diffusivity, sublimation, melting point,
It can be used to adjust dispersibility with binders such as gelatin, reactivity with nucleophilic groups, reactivity with electrophilic groups, etc.

Next, a specific example of EAG will be given.

Examples of aryl groups substituted with at least one electron-withdrawing group include 4-nitrophenyl group, 2-nitrophenyl group, 2-nitro-4-N-methyl-N-n-butylsulfur group, Famoylphenyl group, 2-nitro-4-N-methyl-N-n-octylsulfasoylphenyl group, 2-nitro-4-N-methyl-N-n-
dodecylsulfamoylphenyl group, 2-nitro-4-
N-methyl-N-n-hexadecylsulfamoylphenyl group, 2-nitro-4-N-methyl-N-n-octadecylsulfamoylphenyl group, 2-nitro-4-N
-Methyl-N-(3-carboxypropyl)sulfamoylphenyl group, 2-nitro-4-N-ethyl-N-(
2-Sulfoethyl)sulfamoylphenyl group, 2-nitro-4-N-〇-hexadecyl-N-(3-sulfopropyl)sulfamoylphenyl group, 2-nitro-4-
N-(2-cyanoethyl)-N-((2-hydroxyethoxy)ethyl)sulfamoylphenyl group, 2-nitro-4-diethylsulfamoylphenyl group, 2-nitro-4-di-n-butylsulf famoylphenyl group, 2
-Nitro-4-di-n-octylsulfamoylphenyl group, 2-nitro-4-di-n-octadecylsulfamoylphenyl group, 2-nitro-4-methylsulfamoylphenyl group, 2-nitro- 4-n-hexadecylsulfamoylphenyl group, 2-nitro-4-N-methyl-N-(4-dodecylsulfonylphenyl)sulfamoylphenyl group, 2-nitro-4-(3-methylsulfamoyl phenyl) sulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-butylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-octylsulfamoylphenyl group, 4-nitro-2-N
-Methyl-N-n-dodecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-hexadecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n- octadecylsulfamoylphenyl group,
4-nitro-2-N-methyl-N-(3-carboxypropyl)sulfamoylphenyl group, 4-nitro-2-
N-ethyl-N-(2-sulfoethyl)sulfamoylphenyl group, 4-nitro-2-N-n-hexadecyl-
N-(3-sulfopropyl)sulfamoylphenyl group, 4-nitro-2-N-(2-cyanoethyl)-N-(
(2-hydroxyethoxyethyl)sulfamoylphenyl group, 4-nitro-2-diethylsulfamoylphenyl group, 4-nitro-2-di-n-butylsulfamoylphenyl group, 4-nitro-2-di -n-ofdelsulfamoylphenyl group, 4-nitro-2-di-n-octadecylsulfamoylphenyl group, 4-nitro-2-
Methylsulfamoylphenyl group, 4-nitro-2-n
-hexadecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-(4-dodecylsulfonylphenyl)sulfamoylphenyl group, 4-nitro-2-(
3-methylsulfamoylphenyl) sulfamoylphenyl group, 4-nitro-2-chloropheny) LtjM,
2-nitro-4-chlorophenyl group, 2-nitro-4-
N-methyl-N-n-butylcarbamoylphenyl group,
2-nitro-4-N-methyl-N-n-octylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-
n-dodecylcarbamoylphenyl group, 2-nitro-4
-N-methyl-N-n-hexadecylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-n-octadecylcarbamoylphenyl group, 2-nitro-4-N-
Methyl-N-(3-carboxypropyl)carbamoylphenyl group, 2-nitro-4-N-ethyl-N-(2-
sulfoethyl)carbamoylphenyl group, 2-nitro-
4-N-n-hexadecyl-N-(3-sulfopropyl)carbamoylphenyl group, 2-nitro-4-N-(2
-cyanoethyl)-N-((2-hydroxyethoxy)
ethyl) carbamoylphenyl group, 2. -Nitro-4-
diethylcarbamoylphenyl group, 2-nitro-4-di-n-butylcarbamoylphenyl group, 2-nitro-4
-di-n-octylcarbamoylphenyl group, 2-nitro-4-di-n-octadecylcarbamoylphenyl group, 2-nitro-4-methylcarbamoylphenyl group, 2
-Nitro-4-n-hexadecylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-(4-dodecylsulfonylphenyl)carbamoylphenyl group, 2-nitro-4-(3-methylsulfamoylphenyl group) ) Carbamoylphenyl group, 4-nitro-2-N-methyl-N
-n-butylcarbamoylphenyl group, 4-nitro-2
-N-methyl-N-n-octylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-n-dodecylcarbamoylphenyl group, 4-nitro-2-N-methyl-
N-n-hexadecylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-n-octadecylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-(
3-carboxypropyl) carbamoylphenyl group, 4
-Nitro-2-N-ethyl-N-(2-sulfoethyl)
Carbamoylphenyl group, 4-nitro-2-N-n-hexadecyl-N-(3-sulfopropyl)carbamoylphenyl group, 4-nitro-2-N-(2-cyanoethyl)-N-((2-hydroxyethoxy ) ethyl) carbamoylphenyl group, 4-nitro-2-diethylcarbamoylphenyl group, 4-nitro-2-di-n-butylcarbamoylphenyl group, 4-nitro-2-di-n-octylcarbamoylphenyl group, 4- Nitro-2-di-n-
octadecylcarbamoylphenyl group, 4-nitro-2
-methylcarbamoylphenyl group, 4-nitro-2-n
-hexadecylcarbamoylphenyl group, 4-nitro-
2-N-methyl-N-(4-dodecylsulfonylphenyl)carbamoylphenyl group, 4-nitro-2-(3-
methylsulfamoylphenyl) carbamoylphenyl group, 2,4-dimethanesulfonylphenyl group, 2-methanesulfonyl-4-benzenesulfonylphenyl group, 2
-n-octanesulfonyl-4-methanesulfonylphenyl group, 2-n-tetradecanesulfonyl-4-methanesulfonylphenyl group, 2-n-hexadecanesulfonyl-4-methanesulfonylphenyl group, 2,4-di-n
-dodecanesulfonylphenyl group, 2,4-cytodecanesulfonyl-5-trifluoromethylphenyl group, 2-
n-decanesulfonyl-4-cyano-5-trifluoromethylphenyl group, 2-cyano-4-methanesulfonylphenyl group, 2,4.6-dolycyanophenyl group, 2.
4-dicyanophenyl group, 2-nitro-4-methanesulfonylphenyl group, 2-nitro-4-n-dodecanesulfonylphenyl group, 2-nitro-4-(2-sulfoethylsulfonyl)phenyl group, 2-nitro- 4-carboxymethylsulfonylphenyl group, 2-nitro-4-carboxyphenyl group, 2-nitro-4-ethoxycarbonyl-5-n-butoxyphenyl group, 2-nitro-4-ethoxycarbonyl-5-n-hexadecyl Oxyphenyl group, 2-nitro-4-diethylcarbamoyl-5-n
-hexadecyloxyphenyl group, 2-nitro-4-cyano-5-n-dodecylphenyl group, 2.4-dinitrophenyl group, 2-nitro-4-n-decylthiophenyl group, 3.5-dinitrophenyl group group, 2-nitro-3,5
-dimethyl-4-n-hexadecanesulfonyl group, 4-
Methanesulfonyl-2-benzenesulfonylphenyl group, 4-n-octanesulfonyl-2-methanesulfonylphenyl group, 4-n-tetradecanesulfonyl-2-methanesulfonylphenyl group, 4-n-hexadecanesulfonyl-2-methanesulfonyl Phenyl group, 2,5-
Cytodecanesulfonyl-4-trifluoromethylphenyl group, 4-n-decanesulfonyl-2-cyano-5-trifluoromethylphenyl group, 4-cyano-2-methanesulfonylphenyl group, 4-nitro-2-methanesulfonyl group Phenyl group, 4-nitro-2-n-dodecanesulfonylphenyl group, 4-nitro-2-(2-sulfoethylsulfonyl)phenyl group, 4-nitro-2-carboxymethylsulfonylphenyl group, 4-nitro-2- Carboxyphenyl group, 4-nitro-2-ethoxycarbonyl-5-n-butoxyphenyl group, 4-nitro-2-ethoxycarbonyl-5-n-hexadecyloxyphenyl group, 4-nitro-2-diethylcarbamoyl-5 -n
-hexadecyloxyphenyl group, 4-nitro-2-cyano-5-n-dodecylphenyl group, 4-nitro-2-
n-decylthiophenyl group, 4-nitro-3゜5-dimethyl-2-n-hexadecanesulfonylphenyl group, 4
-Nitronaphthyl group, 2,4-dinitronaphthyl group, 4
-Nitro-2-n-octadecylcarbamoylnaphthyl group, 4-nitro-2-dioctylcarbamoyl-5-(
3-sulfobenzenesulfonylamino) naphthyl group, 2
, 3,4,5.6-pentafluorophenyl group, 2-nitro-4-benzoylphenyl group, 2.4-diacetylphenyl group, 4-nitro-2-trifluoromethylphenyl group, 2-nitro-4- trifluoromethylphenyl group, 4-nitro-3-trifluoromethylphenyl group,
2.4.5-tricyanophenyl group, 3゜4-dicyanophenyl group, 2-chloro-4,5-dicyanophenyl group, 2-bromo-4,5-dicyanophenyl group, 4-methanesulfonylphenyl group, 4-n-hexadecanesulfonylphenyl group, 2-decanesulfonyl-5-trifluoromethylphenyl group, 2-nitro-5-methylphenyl group, 2-nitro-5-n-octadecyloxyphenyl group, 2-nitro-4 -N-(vinylsulfonylethyl)-N-methylsulfamoylphenyl group, 2-methyl-6-nidropenzoxazol-5-yl group, and the like.

Examples of heterocyclic groups include, for example, 2-pyridyl group, 3-
Pyridyl group, 4-pyridyl group, 5-nitro-2-pyridyl group, 5-nitro-N-hexadecylcarbamoyl-2
-pyridyl group, 3,5-dicyano-2-pyridyl group, 5
-dodecanesulfonyl-2-pyridyl group, 5-cyano-
2-pyridyl group, 4-nitrothiophen-2-yl group,
5-nitro-1,2-dimethylimidazol-4-yl group, 3.5-diacetyl-2-pyridyl group, 1-dodecyl-5-carbamoylpyridinium-2-yl group, 5-
Nitro-2-furyl group, 5-nitropentthiazole-
2-yl group, etc.

Next, +Time9-1PUG will be explained in detail.

Time represents a group that may cause the cleavage of a nitrogen-oxygen, nitrogen-nitrogen, or nitrogen-sulfur single bond to release PUG through a subsequent reaction. t does not represent 0 or l.

Various groups represented by Time are known, for example, in JP-A-61-147244, pages (5)-(6) and 61-147244.
No. 236549, pages (8) to (14), patent application 1986-8
Examples include the groups described in No. 8625, pages (36) to (44).

PUG represents a group that is photographically useful as Time-PUG or PUG.

Photographically useful groups include, for example, development inhibitors, halides, development accelerators, nucleating agents, couplers, diffusible or non-diffusible dyes, desilvering accelerators, desilvering inhibitors, silver halide solvents, Compounds, developing agents, auxiliary developing agents, fixing accelerators, fixing inhibitors, image stabilizers, color toning agents, processing dependency improvers,
Halftone dot improver, color image stabilizer, photographic dye, surfactant,
Represents hardeners, desensitizers, contrast agents, chelating agents, optical brighteners, etc., or their precursors.

Since these photographically useful groups often overlap in terms of usefulness, representative examples will be specifically explained below.

Examples of development inhibitors include compounds having a mercapto group bonded to the petero ring, such as substituted or unsubstituted mercaptoazoles (specifically, 1-phenyl-5-mercaptotetrazole, 1-(4-carboxyphenyl)-
5-mercaptotetrazole, 1-(3-hydroxyphenyl)-5-mercaptotetrazole, 1-(3-sulfophenyl)5-mercapttetrazole, 1-(
4-sulfamoylphenyl)-5-mercaptotetrazole, 1-(3-hexanoylaminophenyl)-5
-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, 1-(2-carboxyethyl)-5-
Mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole, 2-(2-carboxyethylthio)-5-mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5 -mercap)--1,2,4-triazole, 2-(2-dimethylaminoethylthio)-5-mercapto-1,3,4-thiadiazole, 1-(4-n-hexylcarbamoylphenyl)-2- Mercaptoimidazole, 3-acetylamino-4-methyl-5-mercapto-1,2,4-triazole, 2-mercaptobenzoxazole, 2-
Mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto-6-nitro-1,3-benzoxazole, 1-(1-naphthyl)-5-mercaptotetrazole, 2-phenyl-5-mercapto-1
, 3,4-oxadiazole, 1-(-3-(3-methylureido)phenyl)-5-mercaptotetrazole, 1-(4-nitrophenyl)-5-mercaptotetrazole, 5-(2-ethylhexane) Noylamino)-2-
mercaptobenzimidazole, etc.), substituted or unsubstituted mercaptoazaindenes (specifically, 6-methyl-4-mercapto-1,3゜3a, 7-titrazaindene, 6-methyl-2-benzyl-4-mercapto) −
1, 3, 3a.

7-chitrazaindene, 6-phenyl-4-mercaptodetrazaindene, 4,6-cymethyl-2-mercapto-1,3,3a, ? -tetrazaindene, etc.), substituted or unsubstituted mercaptopyrimidines (specifically,
2-mercapto-pyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine, 2-mercapto-4-
propylpyrimidine, etc.). Peter compounds capable of producing iminosilver, such as substituted or unsubstituted benzotriazoles (specifically, benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, 5,6-dichlorobenzotriazole, -bromobenzotriazole, 5-methoxybenzotriazole, 5-acetylaminobenzotriazole, 5-n-butylbenzotriazole, 5-nitro-6-chlorobenzotriazole, 5,6-dimethylbenzotriazole, 4,5,6 .7-titrachlorbenzotriazole, etc.), substituted or unsubstituted indazoles (specifically, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole, 3-cyanoindazole, 3-nitroindazole, etc.) -n-
butylcarbamoylindazole, 5-nitro-3-methanesulfonylindazole, etc.), substituted or unsubstituted benzimidazoles (specifically, 5-nitropenzimidazole, 4-nitropenzimidazole,
5,6-dichlorobenzimidazole, 5-cyano-6
-Chlorpenzimidazole, 5-trifluoromethyl-6-chlorpenzimidazole, halogen atom (Br
, 1), etc.). In addition, the development inhibitor is
Due to the reaction following the redox reaction in the development process,
After being released from the redox mother nucleus of the general formula (I), it becomes a compound that has development inhibiting properties, which then changes into a compound that has substantially no or significantly reduced development inhibiting properties. It's okay.

Specifically, 1-(3-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(3-maleinimidophenyl)-5-mercaptotetrazole, 5-(phenoxycarbonyl)benzotriazole, 5-(p-cyanophenoxycarbonyl)benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 5-nitro-3-phenoxycarbonylimidazole, 5 -Phenoxycarbonyl-2-mercaptobenzimidazole, 5-(2,3-dichloropropyloxycarbonyl)benzotriazole, 5-benzyloxycarbonylbenzotriazole, 5-(butylcarbamoylmethoxycarbonyl)benzotriazole, 5-(
butoxycarbonylmethoxycarbonyl)benzotriazole, 1-(4-benzoyloxyphenyl)-5-
Mercaptotetrazole, 5-(2-methanesulfonylethoxycarbonyl)-2-mercaptobenzothiazole, 1-(4-(2-chloroethoxycarbonyl)phenyl)2-mercaptoimidazole, 2-[3-(
Thiophen-2-ylcarbonyl)propylphothio5
-Mercapto-1,3,4-thiadiazole, 5-cinnamoylaminobenzotriazole, 1-(3-vinylcarbonylphenyl)-5-mercaptotetrazole,
5-succinimidomethylbenzotriazole, 2-(
4-succinimidophenyl)-5-mercapto-1゜3.4-oxadiazole, 3-(4-(benzo-1
, 2-isothiazole-3-oxy-1,1-dioxy-2-yl)phenyl)-5-mercapto-4-methyl-1,2,4-triazole, 6-phenoxycarbonyl-2-mercaptobenzoxazole, etc. can be given. Further, the development inhibitor may be an iodine atom. Further, the development inhibitor may be an iodine atom.

Examples of the case where PUG is a silver halide solvent include JP-A-60-163042 and U.S. Pat. No. 4,003,9.
10, 4,378゜424, etc., mercaptoazoles or azolethiones having an amino group as a substituent described in JP-A-57-20253, etc., and more. Specifically, those described in Japanese Patent Application No. 1988-71768 can be mentioned. An example of a case where PUG is a nucleating agent is the part of the leaving group released from the coupler described in JP-A-59-170840.

When PIG is a dye, the dye includes azo dye, azomethine dye, indoaniline dye, indophenol dye, anthraquinone dye, triarylmethane dye, alizarin, nitro dye, quinoline dye, indigo dye, Examples include phthalocyanine dyes. Also included are their leuco forms, those with temporarily shifted absorption wavelengths, and dye precursors.

Further examples include dyes that can be chelated.

The above dyes are described, for example, in the following documents.

U.S. Patent No. 3,880,658, U.S. Patent No. 3°931.1
No. 44, No. 3,932,380, No. 3,932,
No. 381, No. 3,942.987, J. Fabian, H. Hartmann (J, Fabian, 11.
“Light Absorption of Organic Colorants” (Light A
bsorption of OrganicColor
anLs), (Springer Verlag (Spr
(or diffusion-resistant analogues), but are not limited to these.

When PUG is a dye, the dye may have an auxochrome blocked by a cleavable group to temporarily shorten the wavelength. That is, a preferred example is a case where when the compound of general formula (I) reacts with a reducing agent and cleaves PUG through a series of reactions, the original dye is produced. For example, in the case of azo dyes, temporary shortening of the wavelength is achieved by blocking auxochromes such as hydroxyl groups, mercapto groups, or amino groups. Examples of dyes shortened by blocking groups include, for example, U.S. Pat. No. 4,234
, No. 672, No. 4,310,612, No. 3.57
No. 9.334, No. 3,999.991, No. 3,9
No. 94,731 or No. 3.23O, OAS.

Other examples of PIG of general formula (I) of the present invention are disclosed in U.S. Pat.
You can refer to the description in No. 135.

Next, specific examples of the compound represented by the general formula (I) will be shown, but the invention is not limited thereto.

C10) 1:n 1111'137 (CH2)20CH3 :C:C glue work! b 0 n= and) B ♂ p ro ♂ Ell 工ζshi == gu1c1 S:e -l d The method for synthesizing the compound of the present invention is described in Japanese Patent Application No. 61-88625, No. 61-87721, No. 62 -34954 No. 6
No. 2-34953.

The compound represented by the general formula (I) used in the present invention can be used in an emulsion layer or an intermediate layer adjacent thereto which does not contain a photosensitive emulsion.

When the color-sensitive emulsion layer is composed of two or more same color-sensitive layers having different sensitivities, it can be added to any layer such as the high-speed layer, intermediate-speed layer, or low-speed layer. be.

The amount of the compound represented by general formula (I) added is 1 x
10-7 to 1 x 10-'n+ol/rn" is preferred, particularly 1 x 10-6 to 1 x 10-'mol/rn"
m' is preferred. However, depending on the type of PUG, the general formula (
The preferred amount of the compound represented by I) varies.
For example, if PUG is a dye or a ligand, I
()-"-I X 10-'mol/rn"%PUG
1 per mole of silver halide when is a development inhibitor.
It is preferable to use it in the range of x 10-7 to 1 x 10-'mol, particularly preferably txto-i to 1X10-6 to 5X10-2. Further, when PUG is a development accelerator or a nucleating agent, the amount added is preferably the same as that of the above-mentioned development inhibitor. When PUG is a silver halide solvent, IX 10' to IX per mole of silver halide.
It is preferably used in a range of 10-3 mol, particularly preferably in a range of 1x10-4 to 1x10 mol.

In the present invention, the compound represented by the general formula (I) releases a photographically useful group or its precursor by accepting electrons from a reducing substance. Therefore, if a reducing substance is applied uniformly, a photographically useful group or its +ii'r precursor will be uniformly released, and if the reducing agent is changed to an oxidized form in response to development of silver halide, Release occurs in the non-developed area.

The reducing substance used in the present invention may be an inorganic compound or an organic compound, but its oxidation potential is preferably lower than the standard oxidation-reduction potential of silver ion/silver, 0.80V.

Examples of compounds that can be used as reducing substances in the present invention include inorganic reducing agents such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, hydroxamic acids, semicarbazides, and amino acids. , various amines,
Borane-amine complexes, hydroquinones, aminophenols, catechols, P-phenylenediamines, 3
In addition to pyrazolidinones, hydroxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc., T.H. James (T, If, Ja
mes)'s book ``The Theory of the Photographic Process J''.
thePhotographic Process
) 4th edition pages 291-334 can also be used. Also, JP-A-56-138,736, JP-A-56-138,736;
Reducing agent precursors described in US Pat. No. 4,330,617 and the like can also be used.

The reducing substance may be added to the developer, incorporated into the photosensitive material, or added to both.

The compound of general formula (1) of the present invention releases a photographically useful group or its precursor by receiving electrons from a reducing substance. Therefore, if a reducing substance is oxidized in an imagewise manner, the remaining reducing substance in an inverse imagewise manner is utilized.

The reducing substance used in the present invention may be either an inorganic compound or an organic compound, and its oxidation potential is preferably lower than the standard oxidation-reduction potential o, aov of silver ions/silver.

Among inorganic compounds, metals with an oxidation potential of 0.8v or less, such as Mn, Ti, Si, and 2n.

Cr%F, e, Co%Mo, Sn%Pb, KaiH2,
Examples include Sb, Cu, and Hg. In addition, ions with an oxidation potential of 0.8V or less or complex compounds thereof, such as C'2+, v2÷, Cu◆, Fe2÷, Mn042
-1I-1(:o(CN)6'-, Fe(CN)6'-
, or (Fe-EDTA) 2-.

Furthermore, metal hydrides with an oxidation potential of 0.8 V or less, such as NaHlLiH, KH, NaCl, Li
B) I, , LiAl (0LC4119) 31
1, LiAR, (OC113)38, etc. Also, sulfur or phosphorus compounds with an oxidation potential of 0.8V or less, such as Na2503.

NaHS% Na1lSO3, H3P, H251Na2
Examples include S, Na2 S2, and the like.

Reducing substances for organic compounds include organic nitrogen compounds such as aliphatic amines or aromatic amines, organic sulfur compounds such as aliphatic thiols or aromatic thiols, or aliphatic phosphines or aromatic phosphines. Organophosphorus compounds are also suitable, but preferably Ken
dal-Pelz style (T.H. James)
.

If, James) The Theory of the Photographic Process
of the photographic processes
s) 4th, cd-299 page).

Other examples of compounds that can be used as reducing substances in the present invention include inorganic reducing agents such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane,
Amine complexes, hydroquinones, aminophenols,
Catechols, p-phenylenediamines, 3-pyrazolidinones, droxytetrones, ascorbic acid,
In addition to 4-amino-5-pyrazolones, etc., the above-mentioned T.H. James (T, Il, JaI)
les), the reducing agents described in pages 291 to 334 of his book, and the aforementioned JP-A-56-138,736, JP-A-57-40,
Reducing agent precursors described in US Pat. No. 245, US Pat. No. 4,330,617, and the like can also be used.

Examples of more preferable reducing substances include the following.

3-pyrazolidones and their precursors (e.g. 1
-Phenyl-3-pyrazolidone, 1-phenyl-4,4
-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, l-
m-tolyl-3-pyrazolidone, 1-p-tolyl-3-
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis-(hydroxymethyl)
-3-pyrazolidone, 1,4-di-methyl-empty-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1-(3-chlorophenyl)
-4-Methyl-3-pyrazolidone.

1-(4-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-tolyl)-4-methyl-3-pyrazolidone, 1-(2-tolyl)-4-methinov-3-pyrazolidone, 1 -(4-tolyl)-3-pyrazolidone, 1
-'(3-tolyl)-3-pyrazolidone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidone,! −(
2-trifluoroethyl)-4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1.5-
Diphenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-stearoyloxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-lauroyloxymethyl-3-pyrazolidone, 1-phenyl 4゜4-bis -(lauroyloxymethyl)-3-pyrazolidone, 1
-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl-3-acetoxypyrazolidone), hydroquinones and their precursors (e.g. hydroquinone, toluhydroquinone, 2,6-dimethylhydroquinone, t-butylhydroquinone, 2. 5-di-t-butylhydroquinone, t-octylhydroquinone, 2.5-di-t-octylhydroquinone, pentadecylhydroquinone, 5-pentadecylhydroquinone-2-sodium sulfonate, p-benzoyloxyphenol, 2- Methyl-4-benzoyloxyphenol, 2-1-butyl-4-(4-chlorobenzoyloxy)phenol] Hydroquinone Sodium disulfonate, 2-(3
, 5-bis(2-hexyldecanamide)benzamide)hydroquinone, 2-(3-hexadecanamide)benzamidehydroquinone, 2-(2-hexyldecanamide)hydroquinone], paraphenylenediamines color developer 1 example, for example 4
-amino-N,N-diethylaniline, 3-methyl-4
-amino-N, N-diethylaniline, 4-・amino-
N-J ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-butoxyethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline] As a reducing agent for aminophenols, 4-amino- 2
, 6, dichlorophenol, 4-amino-2,6-dibromophenol, 4-amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, 4-amino-2,6-dichlorophenol hydrochloride, etc. There is. Furthermore, Research Disclosure Magazine No. 151, Mo., 1510, U.S. Patent No.
, 021,240, 2,6-dichloro-4-substituted sulfonamidophenol, 2,6-dipromo-substituted sulfonamidophenol, JP-A-59-11674
No. 0 describes p-(N,N-dialkylaminophenyl)sulfamine and the like, which are useful. In addition to the phenolic reducing agents described above, naphthol reducing agents such as 4-amino-naphthol derivatives and 4-substituted sulfonamide naphthol derivatives are also useful. Furthermore, as a general color developer that can be applied, U.S. Pat.
, 895,825, the aminopyrazoline conductors described in U.S. Pat.
On the page (RD-19412, RD-19415),
and dracin derivatives have been described. These color developers may be used alone or in combination of two or more.

Regarding the implementation of the present invention, the functions of the compounds of the present invention in silver halide photographic materials will be explained.

The compound of the present invention is incorporated into a silver halide photographic light-sensitive material by the addition method described below, and is reduced along the electron transfer path represented by the arrow shown in formula (1) below, releasing a photographically useful group. do.

Formula (1) Compound of the present invention Photographically useful group It may be contained in the processing liquid and acted upon, or it may be contained in the sensitive material in advance and acted upon, or it may be contained in the sensitive material in advance and the same or different reducing substance (RE) may be added from the processing liquid. ) may be used.

This reducing substance (RE) is used to reduce silver halide and is consumed depending on the degree of exposure when a commonly used negative silver halide emulsion is used. The reaction requires an amount that corresponds inversely to the degree of exposure, i.e.
Of the supplied reducing substance (RE), only the remaining amount that is not used for reducing silver halide is used.

Therefore, photographically useful groups are released in larger quantities in areas that are less exposed. Furthermore, when an autopositive emulsion is used, the reduction of silver halide occurs on the unexposed side, contrary to the case of a negative emulsion, so that reducing substances are consumed on the unexposed side. Therefore, the reaction between the compound of the present invention and the reducing substance occurs in a larger amount in the exposed area, and a larger amount of photographically useful groups is released.

As described above, the compound of the present invention releases a small amount of photographically useful groups in the developing area (the area where silver halide and a reducing substance react) and a large amount in the non-developing area; A reducing substance called an electron transfer agent (ETA) represented by the following formula (2) is used for the purpose of adjusting the ratio of the emitted amount of photographically useful groups (usually to improve this ratio). It is preferable to use them together.

Formula (2) In formula (2), the electron transfer agent (ETA) can be selected from the above-mentioned reducing substances, and is preferably selected from organic reducing agents. Further, in order for the electron transfer agent (ETA) to have a more favorable effect, it is desirable that the redox potential is located between that of the reducing substance (RE) and the silver halide.

The method for causing the electron transfer agent (ETA) to interact with the reducing substance (RE) is the same as the method described for the reducing substance (RE) in formula (1).

In formula (2), the electron transfer agent mediates the transfer of electrons from the reducing substance to silver halide, but the process of releasing the photographically useful group described in formula (1) is the same. . In formula (2), when the reducing substance is immobile, electron transfer from the reducing substance to the silver halide may be slowed down. As can be understood from the formula (!), when the electron transfer from the reducing substance to the silver halide is slowed down, the reaction between the reducing substance and the compound of the present invention occurs preferentially, so the developing area and the non-developing area are separated. The difference in the amount of photographically useful groups released at .

The electron transfer agent is used to facilitate the transfer of electrons from the immobile reducing substance to the silver halide and to increase the difference in the amount of photographically useful groups released between the developed and non-developed areas. I can do it.

For the above purpose, when the electron transfer agent is used in combination with an immobile reducing substance (RE), it is necessary that the electron transfer agent has greater mobility than the reducing substance (RE). By using an electron transfer agent as shown in formula (2), an immobile reducing substance can be effectively used.

As the reducing substance used in combination with ETA, any reducing agent may be used as long as it does not substantially migrate in the layer of the photosensitive material, but hydroquinones, aminophenols, and aminonaphthols are particularly preferred. kind,
Examples include 3-pyrazolidinones, saccharin and their precursors, picoliniums, and compounds described as electron donors in JP-A-53-110827.

An example is shown below.

S-2 S-35-4 S-5S-7 S-63-8 -tO S-133-14 S-155-16 S-193-20 S-21 S-22S-23 S-245-26 Sui S-29' 5-3O(i
) C[) S-38 S-395-4O Sushi IG n':n - S-465-47 S-493-50 S-523-53 IGr'133 ETA used in combination with these Any material can be used as long as it cross-oxidizes, but preferred are 3-pyrazolidinones, aminophenols, phenylenediamines, and reductones, each of which is diffusible.

Examples of the compound include the following compounds.

3-pyrazolidinones, such as 1-phenyl-3-pyrazolidinone, 4,4-dimethyl-1-phenyl-3-pyrazolidinone, 4-hydroxymethyl-4-methyl-1
-Phenyl-3-pyrazolidinone, 4-hydroxymethyl-4-methyl-1-tolyl-3-pyrazolidinone, 4
-Hydroxymethyl-4-methyl-1-(4'-methoxy)-3-pyrazolidinone, 4,4-bis(hydroxymethyl)-11phenyl-3-pyrazolidinone, 4,4
-bis(hydroxymethyl)-1-tolyl-3-pyrazolidinone, 4.4-bis(hydroxymethyl)-1-(
4'-methoxy)-3-pyrazolidinone, 4,4-dimethyl-1-tolyl-3-pyrazolidinone, 1,5-diphenyl-3-pyrazolidinone, etc.; aminophenols, such as p-aminophenol, P-methylaminophenol , p-dimethylaminophenol, p-dibutylaminophenol, p-piperidinoaminophenol,
4-dimethylamino-2,6-simethoxyphenol, etc.: Phenylenediamines, such as N-methyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine , N, N, N', N'-tetramethyl-P-phenylenediamine, 4-diethylamino-2,6-simethoxyaniline, etc.: Reductones such as piperidinohexose reductone, pyrodinohexose reductone, etc. .

It is also possible to use a precursor that is hydrolyzed under alkaline conditions to produce the above-mentioned compounds.

For example, Japanese Patent Publication No. 55-52055, Japanese Patent Publication No. 54-39
No. 727, Japanese Unexamined Patent Publication No. 57-135949, etc.

When applied to conventional silver halide photosensitive materials, there are two methods for applying the above-mentioned reducing substance or a combination of a reducing substance and ETA to the photosensitive material: supplying it to the photosensitive material during development in the form of a developer, and reducing It is preferable to incorporate the chemical substance into the photosensitive material and supply the ETA in the form of a developer. In the former case, the preferable usage amount is o, ooi mol/It to 1 mol/It as the total concentration in the liquid, and in the case of built-in, 0.5 to 5 mol of the reducing substance per 1 mol of the compound of the present invention. ETA as concentration in liquid 0.001
It is preferable to use mol/2 to 1 mol/IL.

In the present invention, a common developer can be used for developing the photosensitive material.

The developer contains hydroquinone, dihydroxybenzenes such as hydroquinone monosulfonate, and 1-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known developers such as aminophenols such as methyl-p-aminophenol and p-phenylenediamines such as 3-methyl-4-amino-N,N-diethylaniline can be used alone or in combination. These developing agents may, of course, have the properties of functioning as both the above-mentioned reducing agent for PUG release and the ETA compound that works together with the reducing agent, but in other cases, they can be halogenated independently of the reducing agent and the ETA compound. It may also act as a silver developing agent. An example of the latter is a reversal process in which a first development is performed under conditions that do not cause PUG release, and then a PUG release step is performed.

The developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds; Hydroxylamine, triethanolamine, West German patent application (
OLS) No. 2622950, preservatives such as sulfites or bisulfites, organic solvents such as diethylene glycol: benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates, 3. Development accelerator such as 6-thiaoctane-1,8-diol; Dye-forming coupler: Competing coupler:
Nucleating agents such as sodium boron hydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; tackifiers; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid Acetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids such as the compounds described in JP-A-58-195845, l-hydroxyethylidene-
1,1'-diphosphonic acid, organic phosphonic acids described in Research Disclosure 18170 (May 1979), aminotris (methylenephosphonic acid), ethylenediamine-N, N, N', N'-tetramethylene phosphonic acid, etc. Aminophosphonic acid, JP-A-52-1027
No. 26, No. 53-42730, No. 54-121127
No. 55-4024, No. 55-4025, No. 55
-126241, 55-65955, 55-6
No. 5956, and Research Disclosure 18
170 (May 1979), a chelating agent such as a phosphonocarboxylic acid can be contained.

The developing agent is generally at a concentration of about 0.1 g to about 30 g per developer solution IIL, more preferably about 1 g per developer solution IIL.
g - used at a concentration of about 15 g. Further, the pH of the developer is usually 7 or more, and most commonly used at a pH of about 9 to about 13.

According to the present invention, it is possible to lower the pH of the developer.

For this reason, it is possible to increase the concentration of the type of developing agent whose solubility increases when the pH is lowered, which not only extends the life of the processing solution, but also increases the concentration of the developer replenisher, or reduces the amount of replenishment. Disposable development is measured depending on the amount.

Organic solvents may be used as solubilizing agents, ie, those that improve the solubility of developer components, especially the developing agent.

These include ethylene glycol, hexylene glycol, diethylene glycol, methyl cellosolve, methanol, ethanol, acetone, triethylene glycol,
Dimethylformamide, dimethyl sulfoxide, etc. Special Publication No. 1983-33378, Special Publication No. 44-9509
This includes the compounds described in No.

The amount added can vary widely depending on the component composition of the liquid, but is usually 50% or less, often 10% or less of the liquid used. However, the solvent constituting the treatment liquid may be anhydrous.

As salts, NaN0. , KNO3, Na, SO2,
NaCIt, KCffi, borax, NaHCO3, KH
Examples include CO3 and boric acid.

In the present invention, instead of using a developer, a developing agent is included in the photosensitive material, and during processing, a solution having a composition other than the above-mentioned developer excluding the developing agent may be used. Generally, this type of liquid is called an activator, but in this specification, the expression "developer" is used in a broader sense to include activators.

In any case, in the present invention, the development process is performed in the presence of water in an amount exceeding (preferably 1.2 times or more) necessary for the maximum expansion r4 of the coating film of the photosensitive material.

The desilvering step following the development step can be any known bleaching and fixing, bleach-fixing, or combination thereof. Oxidizing agents include polyvalent, metal compounds (e.g. ferricyanides), peroxyacids, quinones, nitroso compounds;
Dichromate; iron(01) or cobalt(III)
organic complex salts (e.g. aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Complex salts with aminopolyphosphonic acid, phosphonocarpanic acid, and organic phosphonic acids); persulfates, hydrogen peroxide, permanganates, and the like can be used. Among these, useful aminopolycarboxylic acids or aminopolyphosphonic acids or salts thereof for forming organic complex salts of iron (m) are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl )-N'
, N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propatol Tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyl iminodiacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminenibrobionic acid, phenylenediaminetetraacetic acid, 2-phosphonobutane-1 , 2,4-triacetic acid, 1,3-diaminopropanol-N,N.

N', N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N', N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N,N,N'.

N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, etc. can be mentioned.

Among these compounds, iron(m) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

As the iron (m) complex salt, a ready-made complex salt of one or more citrons may be used, or iron (m) salts (for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, phosphoric acid) can be used. A ferric ion complex salt may be obtained by reacting a chelating agent (such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) with a chelating agent (such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) in a solution. When forming a complex salt in a solution, one or both of the ferric salt and the chelating agent may be used in combination of two or more. In either case of forming a pre-formed complex salt or forming a complex salt, the chelating agent may be used in an amount greater than the stoichiometric amount.

In addition, the bleach or bleach-fix solution containing the above-mentioned ferric ion complex contains metal ions other than iron such as calcium, magnesium, aluminum, nickel, bismuth, zinc, tungsten, cobalt, copper, and complex salts thereof, or hydrogen peroxide. may be included.

Persulfates for bleaching or bleach-fixing that can be used in the present invention include alkali metal persulfates such as potassium persulfate and sodium persulfate, or ammonium persulfate.

Bleach or bleach-fix solutions may contain rehalogenated bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide). may contain a curing agent. Boric acid if necessary,
One or more inorganic acids and organic acids having pH buffering ability such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and the like; Alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The appropriate amount of bleaching agent per bleaching solution iIL is o.i to 2 moles, and the preferable p+1 range of the bleaching solution is 0.5 to 8.0 in the case of ferric ion complex salts, especially aminopolycarboxylic acid. , 4.0 to 7.0 in the case of ferric ion complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid.
It is. In the case of persulfates, a pH range of 1 to 5 is preferred at a concentration of 0.1 to 2 to 2 molar.

The fixing agents used for fixing or bleach-fixing are known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid, 3 These are water-soluble silver halide dissolving agents such as thioether compounds such as .6-cythia-1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. Furthermore, in the bleach-fixing process, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used.

For fixing or bleach-fixing processing, the fixer concentration is 0.2~
4 mol/fl is desirable. In addition, in the bleach-fixing process, the amount of ferric ion complex salt per bleach-fix solution is 0.1
-2 mol, and the fixing agent preferably ranges from 0.2 to 4 mol.

In addition, the po of the fixing and bleaching solution is usually 4.0 to 9.
0 is preferable, and 5.0 to 8.0 is particularly preferable.

In addition to the above-mentioned additives, the fixer or bleach-fixer contains preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroxylamine, hydrazine, and bisulfite compounds of aldehyde compounds. (for example, acetaldehyde sodium bisulfite). Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained.

The fixing solution described above can be used not only for color photosensitive materials but also for processing black and white photosensitive materials.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Patent No. 1,290,
No. 812, No. 2,059,988, JP-A-53-3
No. 2736, No. 53-57831, No. 53-3741
No. 8, No. 53-65732, No. 53-72623,
No. 53-95630, No. 53-95631, No. 53
-104232, 53-124424, 53-
Compounds having a mercapto group or disulfide group described in No. 141623, No. 53-28426, Research Disclosure Y-No. 17129 (July 1978); thiazoline derivatives such as;
No. 6, JP-A-52-20832, JP-A No. 53-32735
Thiourea derivatives described in No. 1, U.S. Pat. No. 3,706,561;
- Iodide described in No. 16235; West German Patent No. 966.4
10, polyethylene oxides described in JP-A No. 2,748.430; polyamine compounds described in JP-A No. 45-8836; and others JP-A-49-42434, JP-A-4
No. 9-59644, No. 53-94927, No. 54-3
No. 5727, No. 55-26506 and No. 5B-16
The compounds described in No. 3940 and iodine and bromide ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat. No. 3,893,858 and West German Patent Nos. 1 and 2.
Compounds described in No. 90,812 and JP-A-53-95630 are preferred. Additionally, U.S. Patent No. 4,552,83
Compounds described in No. 4 are also preferred. These bleach accelerators may be added to the photosensitive material.

After the fixing step or bleach-fixing step, processing steps such as water washing and stabilization are generally performed.

Various known compounds may be added to the washing process and stabilization process for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid; bactericidal agents and anti-inflammatory agents that prevent the growth of various bacteria, algae, and molds (for example, Journal of Antibacterial and Antibiotics); Anti-bact,
Antifung, Agents) Vol. 11.
No. 5゜p207--223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal"), metal salts such as magnesium salts, aluminum salts, bismuth salts, and alkalis. Metal and ammonium salts, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or West Police Department Photographic Science and Engineering Magazine (Photo, Sci, En
g,).

Compounds described in Vol. 6, pp. 344-359 (1965) may also be added. It is particularly effective to add a chelating agent or a bactericidal agent.

The water washing process is a multi-stage countercurrent water washing of 2M1 or more (for example, 2 to 9
It is common practice to reduce the amount of water used for washing by using a tank. Furthermore, instead of the water washing process, JP-A-57-8! ? A multi-stage countercurrent stabilization treatment step as described in No. 43 may also be implemented. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, adjust MpH (
various buffering agents (e.g. borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, Typical examples include aldehydes such as formalin (used in combination with carboxylic acids, etc.) and formalin. Other chelating agents (inorganic phosphoric acid,
(aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide, anti-piping agent (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactant , optical brighteners, hardener metal salts, and the like may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

In addition, for color photosensitive materials for photography, the normally performed post-fixing (washing - stabilization) process can be replaced with the above-mentioned stabilization process and washing process (water saving process).In this case, the magenta coupler is If necessary, the formalin in the stable solution may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes.
Preferably it is 20 seconds to 5 minutes.

Various treatment liquids in the present invention are used at 10°C to 70°C. A temperature of 25°C to 45°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time.
Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, for saving silver in photosensitive materials, West German Patent No. 2,226,770 or U.S. Patent No. 3,
674,499 or treatment with cobalt or hydrogen peroxide fortification as described in U.S. Pat. No. 3,923,5.
One-bath development, bleach-fixing treatment as described in No. 11 may be performed.

Furthermore, each processing time can be made shorter than the standard time within a range that does not cause any problems, if necessary, in order to speed up the process.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, etc., as necessary.

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. The average grain size of the silver halide grains (in the case of spherical or approximately spherical grains, the grain diameter is taken as the grain size, in the case of cubic grains, the principal is taken as the grain size, and expressed as an average based on the t5i' shadow area) is preferably 2 μ or less, but Particularly preferable is 0
．． It is 4μ or less. The particle size distribution may be narrow or wide.

The shape of these silver halide grains may be cubic, octahedral, dodecahedral, tabular with a high alpect ratio, or may be irregular.

It may also be of a so-called convergence type, as described in British Patent No. 635,841 and U.S. Pat. No. 3.622.318. 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. 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.

In the silver halide grain formation or physicothermal process, 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, etc. may be present.

The silver halide emulsion may be a so-called primitive emulsion which is not chemically sensitized, but it is usually chemically sensitized. For chemical sensitization, the sulfur sensitization method uses active gelatin or a compound containing sulfur that reacts with silver (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines), reducing substances (e.g. primary Reduction sensitization using tin salts, amines, hydrazine derivatives, formamidine sulfines, silane compounds), noble metal compounds (e.g. gold compounds, and complex salts of Group I metals of the periodic table such as platinum, iridium, and palladium) ) can be carried out alone or in combination.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, 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; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate, dextran, and starch derivatives. : Various types of synthetic hydrophilic polymers such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

The photographic material of the present invention 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, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) , activated vinyl compound (1,3,5-triacryloyl-hexahydro-5-triazine, 1,3-
vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-
triazines, etc.), mucohalogen acids (mucochloric acid,
mucophenoxychloric acid, etc.), N-carbamoyltridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.) and heloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2 -naphthanesulfonate, etc.) alone or in combination.

Among these compounds, active vinyl compounds or active halogen compounds can be preferably used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsion dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast Various surfactants may be included for various purposes such as sensitization, sensitization, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols alkylamines or amides, polyethylene oxide adducts of silicone), glycidol conductors (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters of sugars:
Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphate esters, N-acyl-N-alkyl taurines,
Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium Cationic surfactants such as salts, a-ring quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

As the antistatic agent, fluorine-containing compounds are particularly preferably used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Nucleic chairs commonly used for cyanine dyes can also be applied to these dyes as basic heteroartic ring nuclei. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, Benzimidazole nuclei, quinoline nuclei, etc. are applicable.
These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2,4 nucleus having a ketomethylene structure.
5- to 6-membered heterocyclic nuclei such as -dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus can be used. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive 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, a polymer containing alkyl (meth)acrylate, glycidyl (meth)acrylate, styrene, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. as a monomer component can be used.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, aanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion used in the present invention, various compounds other than the compounds of the present invention may be used in combination for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or to stabilize photographic performance. Can be done. Namely, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroimidazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (e.g. Mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-
5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.); For example, thioketo compounds such as oxadorinthione, niazaindenes (
For example, triazaindenes, pentaazaindenes, etc.): benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonamides and the like.

The photographic light-sensitive material of the present invention contains a color image-forming coupler, that is, a compound that can develop a color by oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) during color development processing. You may. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a pallast group in its molecule, or a polymerized coupler. The coupler may be 4-equivalent or 2-equivalent to silver ion.
It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The product of the coupling reaction may also be colorless and include a colorless DIR coupling compound that releases a development inhibitor.

For example, magenta couplers include 5-pyrazolone couplers, pi'razolopenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, pyrazolotriazole couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), etc., and cyanogens, naphthol couplers, and phenol couplers.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course I don't mind V.

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.)
, phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate,
dioctylbutyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate) ), trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone. , β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Special Publication No. 48-30494, Special Publication No. 51-398
No. 53, JP-A-50-102334, JP-A-51-2
No. 5133, JP-A-51-59943, Patent Application No. 61-
162813, Japanese Patent Application No. 187996/1983, Japanese Patent Application No. 189771/1983, West German Patent No. 2830917
The polymeric dispersion method described in US Pat. No. 3,619,195 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

This is described in Japanese Patent Publication No. 7,561/1973.

Known antifading agents can be used in the photographic material of the present invention. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxydiphenol derivatives, and bisphenols.

The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure y-1tem/7643 (December 1978) and ILe+n/8716 (November 1979), and the relevant parts are shown in the table below. Shown all together.

Additive type +1017643 11D187
161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, Pages 23-24 Page 648 Right column - Super sensitizers
Page 649, right column 4 - Brightener
Page 24 5 Antifoggant Pages 24-25 6
Page 49 right column and stabilizer 6 Light absorbers, fillers pages 25-26 Page 649 right column ~ Luther dyes Page 650 left column Ultraviolet absorber 7 Stain inhibitors Page 25 right column Page 650 left-right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column lO binder page 26 Same as above 11 Plasticizer, lubricant page 27 page 650 right column 12 Coating aid,
Pages 26-27 Same as above Surfactant 13 Static Page 27 Same as above Inhibitor ■ Specific effects of the invention According to the present invention, the stability and safety over time of the processing solution, especially the developer can be ensured. Furthermore, the pH in the membrane can be increased when necessary. As a result, the release of photographically useful groups is sufficient, and images with excellent photographic properties can be obtained.

(2) Specific Examples of the Invention Specific examples of the present invention will be described in detail below.

Example 1 A silver halide color photosensitive material having a multilayer structure was prepared by coating the following first layer (lowest layer) to seventh layer (top layer) on a paper support laminated on both sides with polyethylene.
And so.

l-oxy-3,5-
Dichloro-S-triazine sodium salt was used.

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

Processing process Temperature Time <Color developer> A B Water 800 aI
L 800 tall nitrilotriacetic acid-3N
a2. Og 2.0g Benzyl alcohol 14mIt 14 ■I diethylene glycol 10mIL10QI42 Sodium sulfite 2.0g 2.0g Hydroxylamine sulfate 3.0g 3.0g Potassium bromide i, Og 1.
0g Sodium carbonate 30g
5g Sodium hydroxide 1.6g
-potassium picolinate
30gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4 monoaminoaniline sulfate 5.0g 5.
Add 0g water and make 1000 mILlo
oo tanplJ 10.
9 8.5 Bleach-fix solution> Water 40
0+1 ammonium thiosulfate (70% solution) 150 rrr (add sodium sulfite 18g ethylenediaminetetraacetic acid iron (I) ammonium 55g ethylenediaminetetraacetic acid 2Na 5g water
1000+5Itp)1
Table 1 shows the results of photographic properties below 6.70.

Table 1 As is clear from Table 1, the development suppression effect (fogging prevention effect) in non-image areas by the compound (1) of the present invention can be obtained by the stable and safe processing solution of the present invention with a low liquid pH. . In particular, the treatment of the present invention greatly reduced the fogging of the yellow coloring layer, which is prone to fogging, and improved the visual whiteness of the fogged areas.

Example 2 A color photosensitive material 201 was prepared by coating the following first layer (bottom layer) to sixth layer (top layer) on a paper support laminated with polyethylene in which titanium dioxide was dispersed (in the table below). ttrg/rrl represents the coating amount.) In the above, 5OLV is phthalic acid-n-butyl ester, and the ultraviolet absorber is 2-(2-hydroxy-3-
sec-butyl-5-t-butylphenyl)benzotriazole.

This light-sensitive material was exposed with a sensitometer and subjected to the following processing.

The photosensitive material (color paper) produced by the above method was printed and then processed. The treatment steps and composition of the treatment liquid at this time are as follows.

Standard processing steps (1) Development 33℃ 20 seconds (2) Bleach-fixing 33℃ 1 minute 30 seconds (3) Washing with water
25-30℃ 3 minutes (4) Drying 75-80℃
Approximately 2 minutes developing tank liquid> Benzyl alcohol 15ml ethylene glycol 15ml potassium sulfite
2.0g potassium bromide
0.7g Sodium chloride 0
．． 2g potassium carbonate 30.0g hydroxylamine sulfate 3.0g hydroxyethoxyiminodiacetic acid 2g 1-hydroxy-ethylidene-1,1'-diphosphonic acid 1g 3-methyl-4-amino-N-ethyl-N-(β-methanesulfone) Amidoethyl)-aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenzylsulfonic acid derivative 1.0g Sodium picolinate 16.0g Potassium hydroxide
Add 2.0g water to bring the total amount to lfi.

<Bleach-fix tank solution> Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to pH 7.1 with potassium carbonate or glacial acetic acid At the same time, water is added to bring the total volume to IIt.

The results of development showed photographic properties when passed through color photographic paper as shown below.

Sensitivity Light White background density Gradation Highest density material
(Dmin) (Dma
x) 2 0 1 0.05" 1
．． 8"1.9"*The three color densities (status A, R%G%B) were almost the same.

The developing solution formulation used was simply the addition of sodium picolinate to the general-purpose color photographic paper formulation used in each country, so the formulation could be shared with ordinary color photographic paper.

Example 3 Using the photosensitive material and processing solution of Example 2, only the developing time was 20
It was extended from seconds to 3 minutes and 30 seconds. The obtained results almost reproduced the photographic characteristics of Example 2 despite the large extension of the development time. In other words, by incorporating an alkali generation mechanism, ■ the effects of fluctuations in development time can be reduced, ■ common development with conventional shipping image type color photosensitive materials can be performed more easily, and ■ density loss due to overdevelopment can be reduced ( It has been shown that the reducing atmosphere is restored after the development of the exposed area is completed and that PUG (in this case, dye release occurs) can be prevented, among other advantages.

Applicant: Fuji Photo Film Co., Ltd. - Agent: Nozomi Watanabe, Patent Attorney
Yo Ishii - Procedural Neyama Masashi (self-proposal) April 8, 1988 1. Display of the case 1988 Patent Application No. 107569 2. Name of the invention Image forming method 3. Person making the amendment Relationship with the case Patent applicant address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name: <
520) Fuji Photo Film Co., Ltd. 4, Agent 10
1 ff1864-4498 Address 4th floor 6, Chiyoda Iwamoto Building, 3-2-2 Iwamoto-cho, Chiyoda-ku, Tokyo Contents of amendment (1) [Developer solution] on page 23 of the specification, lines 2-11
・・・ ・・・ Raise it. ” to be deleted.

(2) Page 24, lines 11-122 “Action on liquid film”
r? IIi It acts as pus.''

(3) On page 27, line 4 [At about 300 μm,
"If the viscosity is increased by E, it will be corrected to about 1000 μm."

(4) Correct ``minuteke'' in the 5th line from the bottom of page 28 to read ``only r minutes''.

(5) Delete [-in bath development intensification processing] from the 5th to 4th lines from the bottom of page 28.

(6) In the second line from the bottom of page 28, "sample is" is corrected to "use is."

(7) On page 28, second line from the bottom, [to arise,]
Insert "generally in laminar flow thin layer processing" after.

(8) r on page 49, line 4 (r
(Corrected as Time?t J.

(9) r, E G, A J on page 49, line 7
is corrected with rEAGJ.

(lO) "Compounds of the present invention" on page 98, line 1 of the same page are replaced with [compounds (1), (II), (III)]
Correct it with J.

(11) 1 mol on page 99, lines 1 and 7
Correct each J to "mole".

(12) Correct the second line of page 99 to "~5x10-" J to F moles.

(13) "Development accelerator or" on page 99, line 4
Delete.

(14) After "preferable." on page 99, line 5, r I) 'U When G is a development accelerator, the preferred addition amount varies greatly depending on the type of development accelerator, but generally 1
0-@~l O-"mol," is inserted.

(15) [General formula (1) of the present invention] on page 101, lines 5 to 13... A lower value is preferable. ” to be deleted.

(16) "The complex compound" in the second line from the bottom of page 101 is corrected to "metal complex compound J."

(II) Page 103, lines 1-166 “The present invention ・
·· ···Available. ” to be deleted.

(18) Correct "hixadecane" in line 6 of page 106 to "hexadecane".

(19) Page 108, line 8 from the bottom and line 5 from the bottom
Line E "compound of the present invention" is defined as "compound (ri, (II 1
, (■)".

(20) "Equation (1)" on page 109 of the same page is corrected as follows.

Yo Yoro, Su = Year・ -■ 24- 1to<< ″o” @- Denku (21) “Compound of the present invention” on page 110, line 2 and line 7 from the bottom is replaced with “compound (+ ), (11), (I
II) Correct J.

(22) "Equation 1 (2)" on page 111 of the same is corrected as follows.

(23) Insert "(However, one complex-forming compound of the present invention is included)" after "Developer" in the fourth line from the bottom on page 126.

(24) rl "0.4μ" on the 9th line of page 145
Correct as uJ.

(25) Insert the following statement after the table on page 160.

[Although it has already been stated in various places, the main aspects of the present invention are summarized below.

1. Color photographic paper, color negative film, color positive film, color reversal film, monochromatic film and auto-positive type photographic paper and film containing a PtJG-releasing compound in which PUG is a pigment and an alkali generating mechanism.

2. In the above 1, the terms image processing methods such as immersion processing by reducing and replenishing, coating processing, single layer processing, general immersion processing, and transfer method.

3. The combination of the photosensitive material and processing described in item 1 above, in which PLIG is a development inhibitor I) which is a U G-releasing compound, and the processing method described in item 2 above.

4. PUGl that uses PUG as an ultraviolet absorber! (26) In the table on page 162 of the same, "The combination of the photosensitive material and the processing described in 1 and the processing method described in 2 above."

"Compound (1) of the present invention" in the main composition column of the fifth layer is corrected to "Exemplary compound (1)".

(27) In the table on page 163, [Compound (1) of the present invention] in the main composition columns of the third layer and the first layer is corrected to "Exemplary Compound (1)."

(28) In the table on page 169 of the same page, [Compound of the present invention + 32) J in the 5th layer section is replaced with [Exemplary compound (32) J
and correct it.

(29) In the table on page 169, Compound (33)J of the present invention in the third layer section is replaced with [Exemplary Compound (33)J
and correct it.

(30) In the table on page 169, Compound (34)J of the present invention in the first layer section is replaced with [Exemplary Compound (34)J
and correct it.

Claims (5)

[Claims] (1) A silver halide photosensitive material having a photosensitive silver halide emulsion, a compound represented by the following general formula (I), and a basic metal compound that is sparingly soluble in water is placed on a support. An image forming method comprising developing with a processing solution containing a compound that causes a complex formation reaction with metal ions constituting a basic metal compound to release a base. General formula (I) PWR-(Time)-_tPUG {In the above general formula (I), PWR represents a group that releases -(Time)-_tPUG upon reduction, and Time represents a group that releases -(Time)- from PWR. ＿tP
After being released as UG, PUG is formed through subsequent reactions.
represents a group that releases t represents 0 or 1, and PU
G represents a photographically useful group. } (2) The image forming method according to claim 1, wherein the compound represented by general formula (I) is represented by the following general formula (II). General formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ {In the above general formula (II), EAG represents an electron-accepting group. N represents a nitrogen atom, and X represents an oxygen atom (-O-), a sulfur atom (-S-), or a nitrogen atom (▲numerical formula, chemical formula, table, etc. available▼). R^1, R^2 and R^3 each represent a simple bond or a group other than a hydrogen atom. R^1, R^2, R^3, and EAG may be bonded to each other to form a ring. Time represents a group that releases PUG through a subsequent reaction triggered by cleavage of the N-X bond, and t represents an integer of 0 or 1. Further, a solid line in the formula represents a bond, and a broken line represents that at least one of them is bonded. PUG and EAG have the same meaning as described in claim 1. } (3) The compound represented by the general formula (II) has the following general formula (
The image forming method according to claim 2, which is represented by III). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above general formula (III), Y represents a divalent linking group, and R^4 is bonded to represents a group of atoms forming a heterocycle. N, X, EAG, Time, t, and PUG have the same meanings as described in claim 2. } (4) A patent claim in which a processing liquid containing a compound that releases a base by causing a complex formation reaction with metal ions constituting a basic metal compound that is sparingly soluble in water is applied in a thin layer onto a silver halide photosensitive material. The image forming method according to any one of the ranges 1 to 3. (5) The silver halide photosensitive material has the general formula (II) or (
The compound represented by III) contains a basic metal compound that is sparingly soluble in water and a reducing substance, and is imaged in the presence of a reducing substance that has a higher oxidation potential than the reducing substance and is capable of reducing silver halide. Paragraphs 1 to 4 of the patent claims forming
2. The image forming method according to any one of the above.