JPH11316445A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the image preserving property of an image forming part by processing a silver halide color photographic sensitive material with a specified processing solution and making a prescribed amount of the silver halide before the processing remain as a silver salt in the sensitive material after the processing. SOLUTION: A silver halide color photographic sensitive material is processed with a processing solution containing at least one kind of compound represented by formula I, II or the like so that 1-50 wt.% of the silver halide before processing the sensitive material is made to remain as silver salt in the sensitive material after the processing. In the formulae, Q is a group of atoms required to form an N-containing. heterocycle, R1 is H, 1-6C alkyl, cycloalkyl, aryl, a heterocyclic group or amino, R2 and R3 are each H, 1-6C alkyl, hydroxy, carboxy, amino, 1-3C acyl, aryl or alkenyl and A is an n1 -valent heterocyclic residue or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material which has been processed (hereinafter sometimes simply referred to as a light-sensitive material or a light-sensitive material for the sake of simplicity). The present invention relates to an image forming method that does not cause a problem in image storability and can obtain better prints.

[0002]

2. Description of the Related Art In recent years, the London Treaty has been concluded due to the movement of protecting the global environment, and the dumping of photographic processing wastewater into the ocean has been substantially prohibited in Japan since January 1, 1996. For this reason, there has been an effort in the photographic industry to reduce photographic processing waste to a minimum. The fixing solution is also disclosed in JP-A-8-2019.
As described in, for example, Japanese Patent Application Laid-Open No. 97-97, studies on low waste liquefaction and low replenishment have been conducted.

In recent years, the frequency of use of high-sensitivity color negative films having a high silver iodide ratio and a large amount of coated silver has increased.
Further, since the replenishment of the fixing process is being reduced, silver halide tends to remain as unfixed silver in the light-sensitive material in a normal fixing process, so that a so-called fixing defect is likely to occur. When fixing failure occurs, a large amount of silver halide remains in the photographic material, so even after processing, the silver salt changes to black silver due to heat, moisture, light, etc. Silver reacts with residual hypo in the light-sensitive material to form silver sulfide. When such black silver or silver sulfide is generated in the negative film, problems such as a change in the color tone of the photosensitive material after storage and a decrease in image quality after storage occur, and when printing at a later date, Causes serious problems.

[0004] Further, as for the processing of color paper, the demand for low replenishment has been increasing in the same manner as described above. There is a concern that the image storage stability of the material may be reduced.

It has been common knowledge that silver halide is completely removed from the light-sensitive material in order to reduce the amount of replenishment in the fixing process. However, as a result of intensive studies, the present invention achieves stabilization of unfixed silver by using a specific compound and positively leaves a silver salt in a light-sensitive material, thereby improving image storability. succeeded in.

Until now, Japanese Patent Application Laid-Open No. Hei 8-29930 discloses a processing method for leaving a large amount of coated silver in an undeveloped portion other than an image forming portion in a monochrome photosensitive material. However, in the monochrome light-sensitive material which forms an image with silver and does not form an image with a dye, the problem of the image storability of the dye having formed an image in the image forming section which occurs in the color light-sensitive material as described above hardly occurs. The problem is completely different from the invention, and there is no description suggesting the invention.

[0007] Further, the above-mentioned fixing failure of the negative film often occurs unevenly on the film, and when printing on color paper, unevenness on the negative is printed, which is a serious problem. Surprisingly, by using the compound of the present invention, even if a silver salt remains in the processed light-sensitive material, it is possible to obtain a good print without any influence on the transmitted light, and the above-mentioned unevenness can be obtained. The present inventor has found that the problem of defective fixing can be solved at the same time, and constituted the present invention.

As the fixing agent used in the fixing solution, ammonium salts such as ammonium thiosulfate and ammonium thiocyanate are usually used from the viewpoint of clearing time. However, these ammonium salts become ammonia gas when the pH of the fixing solution exceeds 7, give an unpleasant odor, drift around the automatic developing machine, and the working environment is deteriorated, which is becoming a problem. In particular, when the automatic developing machine is installed in a poorly ventilated place such as a food section under the building, a serious problem occurs. However, by applying the processing method of the present invention to a fixing solution having a low ammonium salt ratio, it is possible to obtain a processing method which does not deteriorate the fixability, has no problem in print quality, and has good image storability. And found that one of the preferable embodiments of the present invention could be constituted.

Further, the fixing solution is usually circulated and used in an automatic developing machine processing tank for the purpose of equalizing the temperature of the processing liquid, removing dust in the processing tank, and imparting a stirring effect. However, this circulation increases the contact with the atmosphere and easily oxidizes the fixer, which causes a sulfurization problem, and sulfide adheres to the light-sensitive material, which tends to be a serious problem. further,
From recent economic and pollution perspectives, fixers have tended to be replenished with low replenishment, which has made this problem more and more problematic. In order to solve this problem, if the amount of circulation in the fixing processing tank is reduced, fixing defects will occur. However, by using the processing method of the present invention in combination with an automatic developing machine in which the circulating amount of the fixing processing tank is reduced, the fixability is not deteriorated, there is no problem in print quality and the image storability is good. It was found that a processing method could be obtained, and one of the preferred embodiments of the present invention could be constituted.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an image forming method which is excellent in image storability of an image forming section, and which can perform low replenishment processing, reduce ammonium ions and reduce the amount of circulation of a fixing solution. To provide.

[0011]

The above objects of the present invention are as follows. The silver halide color photographic light-sensitive material is processed with a processing solution containing at least one of the compounds represented by the following general formulas [I] to [V], and the weight of the silver halide before processing of the light-sensitive material is 1 weight. % To 50% by weight of a silver salt remaining in the processed silver halide color photographic light-sensitive material as a silver salt,

[0012]

Embedded image [In the formula, Q represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring (including a condensed 5- to 6-membered unsaturated ring), and R ₁ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 6 alkyl groups, cycloalkyl groups, aryl groups, heterocyclic groups (5 to
A 6-membered unsaturated ring is condensed) or an amino group. ]

[0013]

Embedded image [Wherein, R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. Represent.

A is-(C = X) -N (R) (R '),-
_{(CH 2) n 2 - (} C = X) -N (R) (R '), -
_{(S) m 1 - (C} = X) -N (R) (R '), - (S)
_{m 2 - (CH 2) n} 3 - (C = X) -N (R)
_{(R '), - (S} ) m 3 - (CH 2) n 4 -N (R)
_{(R '), - (S} ) m 4 -N (R) (R'), - (N
_{H) n 5 - (CH 2} ) m 5 - (NH) n 6 - (C = X)
-N (R) (R '), -SS- (C = X) -N (R)
(R '), - SZ or _{n 1} monovalent heterocyclic residue representing the (unsaturated ring 5-6 members including those condensed). Here, R and R ′ are the same as R ₂ and R ₃ , respectively, and X is
S, ＯO, or ＮＲNR ″, Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl group, or —S—B—Y (R ₄ )
(R ₅ ), wherein R ″ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (some having a condensed 5- to 6-membered unsaturated ring may be used) Including)
Or n represents an amino group, and n _{1 to} n ₆ and m _{1 to} m ₅ each represent an integer of 1 to 6. B represents the number 1-6 alkylene group with a carbon, Y is -N <, = C <or represents -CH <, _{R 4} and _{R 5} have the same meanings as _{R 2} and _{R 3,} respectively. However _{R 4} and _{R 5} may each represent -B-SZ, also _{R 2} and _R 3, R and R ', _{R 4} and _{R 5} may be bonded to each other to form a ring. ]

[0015]

Embedded image [In the formula, Q ₁ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring (including a condensed 5- to 6-membered unsaturated ring), and R ₁₁ ′ represents a hydrogen atom, an alkali metal atom. ,

[0016]

Embedded image Or an alkyl group. However, Q 'has the same meaning as that of _{Q 1.} ]

[0017]

Embedded image [In the formula, n ₂ , n ₃ , and n ₄ represent integers of 0 to 5. X represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an acyl group.
M represents a hydrogen atom or an alkali metal. R ₂₁ has 1 carbon atom
And represents a substituted or unsubstituted alkyl group or hydrogen atom.
In addition, the disulfide dimer of this compound is also included. ]

[0018]

Embedded image [In the formula, Z ₁ and Z ₂ represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an amino group, a carboxyl group, a sulfonic acid group, or a hydroxyl group. _{n 5, n 6, n 7} , n 8, n 9 is an integer of 0-5. ]

2. 2. The image forming method for a silver halide color photographic light-sensitive material as described in 1, wherein the processing solution is at least one selected from a processing solution having a bleaching ability, a processing solution having a fixing ability, and a stabilizing processing solution. Method,

3. 3. The image forming method for a silver halide color photographic light-sensitive material according to the above item 2, wherein the processing solution is a bleaching solution and / or a fixing solution.

4. The content of the compounds represented by the general formulas [I] to [V] with respect to the treatment solution is 0.0001 mol /
The method for forming an image of a silver halide color photographic light-sensitive material according to any one of the above items 1 to 3, wherein the amount is at least 0.1 mol / liter.

5. The processing solution is a fixing solution, and the replenishing amount of the fixing solution is 900 ml per 1 m ^{2 of the} photosensitive material to be processed.
The above-mentioned items (1) and (3), wherein the amount is 100 ml or more.
Or the image forming method of the silver halide color photographic light-sensitive material according to 4,

6. 5. The silver halide color as described in 1, 3 or 4, wherein the processing solution is a fixing solution, and the ratio of ammonium ions to all cations in the fixing solution is 0 mol% or less, including 0%. Image forming method of photographic photosensitive material,

[7] When the processing liquid is a fixing liquid and the volume of the fixing processing tank is A liter and the circulation amount of the fixing liquid is B l / min, the circulation ratio B / A of the fixing liquid processing tank is 0.2 to 0. 8. The method for forming an image on a silver halide color photographic light-sensitive material as described in 1, 3, or 4 above,

8. Wherein the silver halide color photographic light-sensitive material contains at least one silver halide emulsion having tabular silver halide grains having an aspect ratio of 5 or more in at least 50% of the total projected area. An image forming method for a silver halide color photographic light-sensitive material according to any one of claims 1 to 7,

9. The weight ratio of the total lipophilic photographic material / the total gelatin in the silver halide color photographic light-sensitive material is 0.5.
0 to 0.70, and the total gelatin coating amount is 14.0.
g / m ² or more and 18.0 g / m ² or less, the method for forming an image of a silver halide color photographic light-sensitive material according to any one of the above 1 to 7,

10. The method for forming an image of a silver halide color photographic light-sensitive material according to any one of the above 1 to 7, wherein the calcium content in the silver halide color photographic light-sensitive material is 5 ppm or more and 50 ppm or less,

11. The halogen according to any one of the above items 1 to 10, wherein the silver chloride content of at least one layer of the silver halide emulsion in the silver halide color photographic light-sensitive material is at least 80 mol% including 100%. Image forming method of silver halide color photographic light-sensitive material,

12. When the coating amount of silver halide in the silver halide color photographic light-sensitive material is 200 to 700 mg / m
^2. The image forming method for a silver halide color photographic light-sensitive material according to the above item 11, wherein

13. Wherein the silver iodide content of at least one layer of the silver halide emulsion in the silver halide color photographic light-sensitive material is 0.5 to 10 mol%.
An image forming method for a silver halide color photographic light-sensitive material according to any one of claims 10 to 10,

14. 14. The image forming method for a silver halide color photographic light-sensitive material as described in 13 above, wherein the coating amount of silver halide in the silver halide color photographic light-sensitive material is ² to 7 g / m ^2. Is done.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below. The compounds represented by formulas [I] to [V] used in the present invention will be described. Specific examples of the compounds represented by formulas [I] to [V] used in the present invention are shown below.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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V-1 HO-CH₂CH₂-S-CH₂CH₂-S-
CH₂CH₂-OH V-2 HOOC-CH₂CH₂-S-CH₂CH₂−
S-CH₂CH₂-COOH V-3 CH₃CH₂-S-CH₂CH₂-S-CH₂
CH₃ V-4 CH₃-CH₂CH₂-S-CH₂CH₂-S
-CH₂CH₂-CH₃ V-5 NH₂-CH₂CH₂-S-CH₂CH₂-S
-CH₂CH₂-SO ₃HV-6 HO-CH₂CH₂-S-CH₂CH₂-S-
CH₂CH₂-S-CH₂CH₂-OH V-7 HO-CH₂CH₂CH₂-S-CH₂CH₂
-S-CH₂CH₂-OH V-8 HO-CH₂CH₂-S-CH₂CH₂CH₂
-S-CH₂CH₂-OH

Among the above compounds, compounds preferably used for the purpose of the present invention include I-2, II-2, compounds represented by the general formula [III], IV-1, IV-3,
IV-5 and compounds represented by the general formula [V].

Among the compounds represented by the general formula [III], III-9, III-10, III-13 and III-
V-1 and V-2 are preferably used among the compounds represented by 22, 22, and 23 and the general formula [V]. Particularly preferably used are III-10 and III-1.
3, III-23 and V-1. These compounds may be used alone or in combination of two or more. Also, in order to further exert the effects of the present invention,
It is preferably added to two or more treatment liquids. When added to two or more types of processing solutions, different types of additives may be used. Among the compounds represented by the general formulas [I] to [V] (hereinafter also referred to as compounds of the present invention),
Particularly preferably used in the present invention is a compound represented by the general formula [I
II].

The compound of the present invention has an adsorptive power with silver halide to form a complex compound with silver halide.
Moisture and light cause the silver salt to change to black silver, silver halide reacts with residual hypo in the photographic material to form silver sulfide, and a small amount of color developing agent remaining in the photographic material after processing It is possible to prevent the occurrence of stains, and to obtain a good print without any influence on the transmitted light.

In the present invention, the processing solution to which the compound of the present invention is added may be any processing solution used for processing a silver halide photographic light-sensitive material. More preferably, the compound of the present invention is added to any of the processing solutions having the processing solution having the bleaching ability, the processing solution having the fixing ability, and the stabilizing processing solution. Most preferably, the compound of the present invention is added to either a processing solution having a bleaching ability or a processing solution having a fixing ability.

When the compound of the present invention is used in a processing solution having a bleaching ability, the amount of the compound of the present invention is 0.0001 mol / l to 0.
It is preferably in the range of 1 mol / l, more preferably 0.1 mol / l.
It is more preferably in the range of 005 mol / l to 0.07 mol / l, most preferably 0.01 mol / l.
1 to 0.05 mol / l. When the compound of the present invention is used in a processing solution having a fixing ability, the amount of the compound of the present invention is, from the viewpoint of the effect and the precipitation property of the present invention,
It is preferably in the range of 0.0001 mol / l to 0.1 mol / l, and more preferably 0.001 mol / l to 0.1 mol / l.
It is more preferably in the range of 0.05 mol / l, most preferably 0.005 mol / l to 0.03 mol / l.
1 range. When the compound of the present invention is added to the treatment solution for stabilization, the amount of the compound of the present invention to be added is preferably 0.0001 mol / l from the viewpoint of the effect of the present invention and the precipitation property.
The range is preferably 0.1 mol / l, more preferably 0.0005 mol / l to 0.03 mol / l, and most preferably 0.001 mol / l.
mol / l to 0.01 mol / l.

Further, the effects of the compounds of the present invention are made more remarkable, and the compounds of the general formulas (F-1) to (F-1)
It is preferable that at least one of the compounds represented by 3) is contained. These compounds may be used in combination. As the salt of the compound represented by the general formula (F-1),
Examples thereof include inorganic acid salts such as hydrochloride, sulfate and nitrate, organic acid salts such as phenol salt, double or complex salts with metal salts, hydrated salts, and intramolecular salts.

The compound represented by formula (F-1) is specifically described in Beilsteins: Handbuch der.
Organischen Hemy (Beilsteins H
andbuch der Organishen Ch
emie), Volume II, Vol. 26, pp. 200-212. Among them, those soluble in water are preferred in the present invention. The following are representative examples.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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The amount of the compound represented by the formula (F-1) is preferably 0.1 to 20 g per liter of the processing solution. In the general formula (F-2), Z ₄ represents an atomic group necessary for forming a substituted or unsubstituted carbocycle or a substituted or unsubstituted heterocycle, wherein the carbocycle and heterocycle are monocyclic; May also be a condensed ring, preferably Z ₄
Is an aromatic carbocyclic or heterocyclic ring having a substituent. The substituent of Z ₄ is an aldehyde group, a hydroxyl group,
An alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), an aralkyl group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), a halogen atom,
Nitro group, sulfo group, carboxy group, amino group (for example, N, N-dimethylamino, N-ethylamino, N-
Phenylamino, etc.), hydroxyalkyl group, aryl group (eg, phenyl, p-methoxyphenyl, etc.), cyano group, aryloxy group (eg, phenoxy, p-
Carboxylphenyl), acyloxy group, acylamino group, sulfonamide group, sulfamoyl group (for example, N
-Ethylsulfamoyl, N, N-dimethylsulfamoyl, etc.), carbamoyl group (for example, carbamoyl, N
-Methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.) or a sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.) is preferred.

The carbon ring represented by Z ₄ is preferably a benzene ring, and the hetero ring represented by Z ₄ is preferably a 5- or 6-membered heterocyclic ring. For example, thiophene, pyrrole, Furan, thiazole,
Examples thereof include imidazole, pyrazole, succinimide, triazole, and tetrazole. Examples of the six-membered ring include pyridine, pyrimidine, triazine, and thiadiazine.

Examples of the condensed ring include naphthalene, benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole, quinoline and the like. Preferred examples of the compound represented by formula (F-2) are shown below.

[0058]

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Exemplified compounds (F-2-1) to (F-2-5)
2) is obtained by inserting various substituents into 1 to 6 in the above formula as follows.

[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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Among the specific examples of the compound represented by the formula (F-2), a more preferred compound is (F-2)
-2), (F-2-3), (F-2-4), (F-2-
6), (F-2-23), (F-2-24), (F-2
-52), and most preferably (F-2-
3). The compound represented by formula (F-2) can be easily obtained as a commercial product. The addition amount of the compound represented by the general formula (F-2) is 0.05
To 20 g is preferable, more preferably 0.1 to 15 g, and particularly preferably 0.5 to 10 g.

In the general formula (F-3), Z ₅ and Z ₆
Is a nitrogen atom in the general formula (F-3),
It is preferably a non-metallic atom group necessary to form a ring which can formally form an aromatic ring as an aromatic ring or a tautomer together with ₂ and X ₃ or a nitrogen atom, X ₄ and X ₅ . Z
₅ is a group of non-metallic atoms necessary to form a nitrogen atom, X ₂ and X _{3 in the} general formula (F-3) together with an aromatic ring or a ring capable of forming an aromatic ring in a formal form as a tautomer; And Z
₆ is a nitrogen atom, more preferably a non-metallic atomic group necessary for forming a non-aromatic ring together with X ₄ and X _5.
5-membered ring is preferred as the ring that can be formed is of the form on the aromatic ring as an aromatic ring or a tautomer formed by Z _5, more preferably a pyrazole ring, a triazole ring (1,2,4
-Triazole ring and 1,2,3-triazole ring),
It is a urazole ring. The aromatic ring formed by Z _6, pyrrolidine ring, piperidine ring, morpholine ring and piperazine ring are preferred. Specific examples of the compound represented by Formula (F-3) are shown below.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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In the present invention, the processed light-sensitive material contains silver halide in an amount of 1% by weight or more and 50% by weight or less of the coated silver halide. The amount of the silver halide is from 2% by weight to 30% by weight of the coated silver halide in view of the effect of the present invention.
Or less, more preferably 2% by weight or more and 15% by weight or less. Further, a magnetic recording layer may be provided on the non-emulsion surface of the photosensitive material.

The coated silver halide of the light-sensitive material to be processed includes silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochloride and the like. In the case of a photographic light-sensitive material, it is preferable that the silver iodide content is 0.5 mol% to 10 mol% of the total silver halide. Further, it is more preferable that the photosensitive material has a silver iodide content of 3 mol% to 8 mol% of the total silver halide.

In the case of color paper, high silver chloride is preferably used. The silver chloride content of the emulsion of the light-sensitive material is preferably 80 mol% or more, more preferably 90 mol% or more, and more preferably 99 mol% or more of the total silver halide.
Most preferably, it is at least mol%.

The amount of silver applied to the light-sensitive material to be processed is 2000 m for a silver iodide having a high silver iodide content.
preferably g / ^{m 2} or more 7000 mg / ^{m 2} or less, further 4000 mg / ^{m 2} or more 6000 mg / m
More preferably, it is ² or less.

For a light-sensitive material having a high silver chloride content,
The amount of silver applied is 200 mg / m ² or more and 700 mg / m
² or less, preferably 400 mg / m ² or more 6
More preferably, it is not more than 00 mg / m ² .

Preferred specific processing steps of the processing method according to the present invention are shown below. (1) Color development → bleaching → fixing → washing with water (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Color developing → bleaching → fixing → first stable → first Bistability (5) Color development → bleach → bleach-fix → washing (6) Color development → bleach → bleach-fix → washing → stable (7) Color development → bleach → bleach-fix → stable (8) Color development → bleach → bleach-fix → First stable → Second stable (9) Color development → Bleaching → Bleaching and fixing → Fixing → Washing → Stable (10) Color developing → Bleaching → Bleaching and fixing → Fixing → First stable →
Second stability (11) Color development → bleach-fix → stable (12) Color development → bleach → first fix → second fix → stable (13) Color development → bleach → fix → first stable → second stable →
Third stable Among these steps, (3), (4), (7), (1)
0), (11), (12), and (13) are preferable, and (3) and (11) are particularly preferable.

In the present invention, it is preferable to introduce the processing solution pumped out of the stabilization tank into the processing tank immediately before the stabilization step, from the viewpoint of not only reducing the amount of waste liquid but also improving image storability.

The replenishment amount in the fixing process in the present invention is preferably 900 ml or less per m ² of the photographic material. In addition, 100 ml or more and 900 ml or less, and 35
It is preferably from 0 ml to 700 ml, and most preferably from 400 ml to 600 ml.

The ratio of ammonium ions to all cations in the fixing solution of the present invention is preferably 50 mol% or less, including 0%, more preferably 30 mol% or less, and more preferably 10 mol% or less. Most preferred from the viewpoint of the invention.

The circulation ratio of the fixing processing tank of the present invention is 0.2 mi.
0.8 mi from n ^-1 (also called round / min)
n− ¹ , preferably 0.4 mi
More preferably, it is in the range of n- ¹ to 0.6 min- ¹ . Here, the circulation ratio indicates the ratio of the circulation amount of the processing liquid to the tank capacity.

In carrying out the present invention, the color developing step, the step having a bleaching ability, the step having a fixing ability, and the stabilizing step may be constituted according to a usual method. For example, the color developing step is described in JP-A-5-224373, the step having bleaching ability is described in JP-A-9-90579, the step having fixing ability, and the stabilizing step is described in JP-A-8-201997. No.

The tabular silver halide (hereinafter also referred to as “tabular grain”) in the present invention refers to a circle having two parallel main planes and a circle equivalent diameter of the main plane (a circle having the main plane and a projected area). Is the ratio of the distance between the main planes (i.e., the thickness of the particles), that is, particles having an aspect ratio of 5 or more. In the rapid development processing, it is preferable that 50% or more of the total projected area of all the grains of the tabular grains of the present invention are tabular grains having an aspect ratio of 5 or more, and more preferably 8 or more.

The diameter of the tabular grains of the present invention is preferably from 0.3 to 10 μm, more preferably from 0.5 to 5.0 μm, further preferably from 0.5 to 5.0 μm, in order to obtain a desired sensitivity.
2.0 μm. The particle thickness is preferably 0.05 to
0.8 μm, more preferably 0.1 to 0.3 μm
It is. It has been found that the surface area range according to the diameter and the particle thickness is suitable for rapid development processing. The measurement of the particle diameter and the particle thickness in the present invention is described in U.S. Pat.
226 can be determined.

The size distribution of the tabular grains of the present invention is obtained by dividing the coefficient of variation of the circle-converted diameter of the main plane (the diameter of a circle having the same projected area as the main plane) by dividing the standard deviation of the diameter distribution by the average diameter. ) Is preferably 30% or less, and 20%
It is more preferred that:

The intergranular distribution of the silver iodide content of the silver halide grains of the present invention is obtained by dividing the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content grain distribution by the average silver iodide content). Is preferably 30% or less, more preferably 20% or less.

The tabular grains of the present invention have at least two or more phases having different halogen compositions inside the grains, and the layer having the largest silver iodide content except the outermost layer has a silver iodide content of 3%. It is from mol% to less than 15 mol%, preferably from 3 mol% to less than 10 mol%, more preferably from 5 mol% to less than 8 mol%. Further, the volume fraction of the phase in the particles is preferably 30% or more and 90% or less, more preferably 30% or more and 60% or less. The silver iodide content of the outermost layer of the tabular grains of the present invention is 6%.
It is preferably not less than mol% and not more than the solid solution limit. If it is less than 6 mol%, the storage stability of the adsorption of the sensitizing dye is undesirably reduced.

The outermost layer referred to in the present invention is a region including the surface area of the particles, but it is not always necessary to completely cover the inner phase. Further, the outermost layer in the present invention refers to a region having a thickness of at least 10 atomic layers or more. In the present invention, the silver iodide content on the grain surface refers to a value measured by the XPS method or a value measured by the ISS method, and either may be used.

The surface silver iodide content according to the XPS method of the present invention is determined as follows. Samples were 1 × 10 ⁻⁸ torr
It was cooled to -115 ° C or lower in the following ultra-high vacuum, and irradiated with MgKα as an X-ray for a probe at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d, I
It measures about 3d3 / 2 electron. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the surface is determined from the intensity ratio.

The structure relating to the halogen composition in the grains is represented by X
It can be examined by a line diffraction method, a composition analysis method using EMPA, or the like. Further, the maximum silver iodide-containing phase excluding the outermost layer in the present invention does not include a high iodine-localized region generated by an operation described later for forming dislocation lines.

As a method for producing tabular grains, methods known in the art can be appropriately combined. For example, Japanese Patent Application Laid-Open Nos. 61-6643, 61-146305, and 6
2-157024, 62-18556, 63-
No. 92942, No. 63-151618, No. 63-16
No. 3451, No. 63-220238, No. 63-311
A known method such as that described in Japanese Patent No. 244/244 can be referred to. For example, a double jet method, a double jet method, a so-called controlled double jet method which maintains a constant pAg in a liquid phase in which silver halide is formed, which is one type of the double jet method, and a soluble silver halide having a different composition, A triple jet method, which is independently added, can also be used. A forward mixing method can be used, and a method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. If necessary, a silver halide solvent can be used. Silver halide solvents often used include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Patent Nos. 3,271,157 and 3,790,387
No. 3,574,628 and the like. The mixing method is not particularly limited, and a neutral method using no ammonia, an ammonia method, an acidic method, or the like can be used. However, in order to reduce fog of silver halide grains, it is preferable to use a pH (hydrogen) method. The logarithmic value of the reciprocal of the ion concentration) is 5.5 or less, more preferably 4.5 or less.

The silver halide grains of the present invention contain iodide ions. In this case, the method of adding iodide ions during grain growth is not particularly limited, and they may be added as an ionic solution such as potassium iodide. Further, for example, it may be added as silver iodide fine particles.

The grain formation using silver halide fine grains is as follows.
Grain growth may be carried out using only silver halide fine grains as in the grains disclosed in JP-A-1-183417, JP-A-1-183644, JP-A-1-183645, etc.
What is necessary is just to supply at least one of the halogen elements by silver halide fine particles. In this case, the iodide ions are preferably supplied by silver halide fine particles. As claimed in Japanese Patent Application No. 3-218608, the number of silver halide fine grains used for grain growth is two or more, and even if at least one of them is composed of only one kind of halogen element, Good.

An emulsion containing silver halide grains grown in the presence of silver halide grains having a lower solubility than the growing silver halide grains, as in the claims of JP-A-2-16737. It is particularly preferable to use silver iodide as the silver halide grain having a small solubility product.

The dislocation of tabular grains is described, for example, in J. Am. F. Ha
Milton, Photo. Sci. Eng. , 11
(1967); 57 and T. Shiozawa, Jo
u. of Photo. Sci. Japan, 35 (19
72), p. 213, that is, direct observation using a transmission electron microscope at a low temperature. That is, silver halide grains taken out so as not to apply enough pressure from the emulsion to generate dislocations on the grains are placed on a mesh for an electron microscope to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough.
The use of an electron microscope (200 kV) for a thickness of 25 μm allows observation to be made more clearly. From the grain photograph obtained by such a method, the position and number of dislocations for each grain when viewed from a direction perpendicular to the main plane can be determined.

The position of the dislocation of the grains of the present invention does not necessarily have to be a specific location, but preferably exists at the fringe portion of the tabular grains. It may be present both in the fringe portion of the particle and inside the particle.

The fringe portion of the tabular grains referred to in the present invention refers to the outer periphery of the tabular grains. More specifically, the fringe portion is defined by a perpendicular drawn from the center of gravity of the tabular grain projected surface as viewed from the main plane to each side of the grains. Outside of 50% of the length of the perpendicular (side), preferably outside of 70%, more preferably 8
It means a region outside 0%.

The number of dislocations in the tabular grains of the present invention is preferably such that grains containing 5 or more dislocations account for at least 50% of the projected area of all silver halide grains in the emulsion.
It is particularly preferred that it is 0% or more. Further, the number of dislocations is more preferably 10 or more. In the present invention, the presence of dislocation lines has an advantageous effect on high sensitivity, pressure resistance, and processing stability. When the number of dislocation lines is less than 5, the effect is small, and the number of dislocation lines is preferably large and there is no upper limit.

When dislocation lines exist in the inside of the grain and in the fringe portion, it is preferable that five or more dislocation lines exist in the inside of the grain, and it is more preferable that five or more dislocation lines exist in both the fringe portion and the inside of the grain.

The method of introducing dislocation lines according to the present invention is not particularly limited, but a method of adding an aqueous solution of an iodide ion such as potassium iodide and a water-soluble silver salt solution by a double jet at the position where the dislocation is to be introduced, or A method of adding silver halide fine particles, a method of adding only an iodine ion solution,
The method can be carried out by a method using an iodide ion releasing agent as described in No. 11781. A method of adding an aqueous iodide ion solution and a water-soluble silver salt solution by a double jet,
A method of adding silver iodide fine particles and a method of using an iodide ion releasing agent are preferable, and a method of using silver iodide fine particles is more preferable. The aqueous solution of iodide ions is preferably an aqueous solution of an alkali iodide, and the aqueous solution of a water-soluble silver salt is preferably an aqueous solution of silver nitrate. The dislocation is preferably introduced after the formation of the maximum silver iodide-containing phase inside the grain, and more preferably after the formation of the phase and before the formation of the adjacent phase. Further, in relation to the position of the whole grain, it is preferable that the silver is introduced in an amount corresponding to 50 to 95% of the silver amount of the whole grain, and it is more preferable that the silver is introduced in a proportion of less than 60 to 80%.

The lipophilic photographic material in the present invention refers to a substantially water-insoluble material, and specifically includes a so-called high-boiling solvent and the same as the high-boiling solvent to be added to a photographic light-sensitive material. At the same time or at the same time. For example, an emulsified dispersion to be added to a hydrophilic colloid binder such as an ultraviolet absorber, an anti-turbidity agent, an antioxidant, an anti-stain agent, and an oil-soluble coupler or a DIR coupler is also included. As an organic high-boiling compound, the boiling point at normal pressure is 180 ° C or more and 350 ° C.
Less than is common.

In the present invention, any known method can be used to add a lipophilic photographic material. Typical methods include, for example, one or more of the above-mentioned organic high-boiling compounds and the like. Is dissolved with a photographic additive as described below, if necessary, and, if necessary, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, dimethylene glycol. Dissolve in low boiling solvents such as monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, ethyl alcohol, propyl alcohol, fluorinated alcohol, acetonitrile, dimethylformamide, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone ( The boiling solvent may be used alone or as a mixture.) Anionic surfactants such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and / or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate. The mixture is mixed with an aqueous solution containing a hydrophilic colloid substance such as gelatin containing an emulsifying agent, and emulsified and dispersed by a high-speed rotary mixer, a colloid mill or an ultrasonic dispersing device, and the obtained dispersion is applied to a coating liquid containing a hydrophilic colloid substance. It may be added and coated on a support or on a silver halide emulsion layer or the like coated on the support. The compound capable of forming a certain kind of oil droplet may be dissolved, for example, in the above-mentioned low-boiling organic solvent, and the solution may be directly added to a coating liquid containing a hydrophilic colloid substance. The low-boiling organic solvent used at this time evaporates after coating and drying, and hardly exists in the binder.

The oil-soluble couplers include a yellow coupler, a magenta coupler and a cyan coupler which form a color image by color development. As the couplers that can be used in the present invention, the compounds described in the following patents are representatively included.

Among them, yellow couplers include benzoylacetanilide type, pivaloylacetoanilide type,
Alternatively, it is a 2-equivalent yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction (a so-called split-off group). As the magenta coupler, 5-pyrazolone,
A pyrazolotriazole-based, pyrazolino-benzimidazole-based, indazolone-based, or 2-equivalent magenta coupler having a split-off group.

Further, the cyan coupler is a phenol-based, naphthol-based or 2-equivalent cyan coupler having a split-off group.

Further, as the coupler to be contained in the oil droplet in the present invention, a so-called Weiss coupler which is oil-soluble and does not form a colored dye by reacting with the oxidized form of the developing agent is also a preferred example.

The lipophilic photographic material in the non-photosensitive layer contains an anti-turbidity agent. Examples of the color turbidity inhibitor include compounds described in Japanese Patent Application No. 4-19048, which react with an oxidized form of a color developing agent and do not impart image density.
Specifically, hydroquinone-based compounds (Japanese Patent Application No. 4-19 / 1992)
No. 048 H-1 to H-18), pyrogallol-based compounds, catechol-based compounds (Japanese Patent Application No. 4-19084, P1 to P1)
6), sulfonylamino compounds (Japanese Patent Application No. 4-1904)
No. 8 S-1 to S-19), coupling type compound (CP
-1 to CP-23) and a hydrazine compound (HZ-1)
To HZ-14).

In the present invention, the weight ratio of total lipophilic photographic material / gelatin is preferably 0.50 to 0.70, more preferably 0.50 to 0.65. The preferred gelatin coating amount is 14.0 to 18.0 g / m ² , and more preferably 15.0 to 17.0 g / m ² .

The non-photosensitive layer of the present invention is a layer containing no photosensitive silver halide, but may contain a non-photosensitive silver halide. The non-light-sensitive intermediate layer located between the light-sensitive layers may be the same color-sensitive layer or a different color-sensitive layer, and the weight ratio of at least one lipophilic photographic material / gelatin weight of the non-light-sensitive intermediate layer Is 0.30 or more and 0.90 or less, more preferably 0.35 or more.
70 or less. In the present invention, the weight ratio of the lipophilic photographic material / gelatin in the non-photosensitive intermediate layer is 0.30.
It is not less than 0.90 and more preferably not less than 0.35 and not more than 0.70. If it is more than 0.90, the adhesion of the coating film will decrease and sweating will occur, and if it is less than 0.30, the effect of improving the pressure resistance of the present invention will be small.

In the present invention, the photosensitive layer and the non-photosensitive layer adjacent to each other may be above or below the photosensitive layer as viewed from the support, and all the parent layers of the adjacent photosensitive layer and non-photosensitive layer may be used. Oil-based photographic material weight / gelatin weight ratio difference between 0 and 0.5
0 or less, more preferably 0 or more and 0.40 or less. If it is larger than 0.50, the adhesiveness of the coating film is inferior and the stability over time is also reduced. Further, all the layers adjacent to each other may be photosensitive layers, non-photosensitive layers, or a photosensitive layer and a non-photosensitive layer. The difference in gelatin weight ratio is 0 or more and 0.60 or less, more preferably 0 or more and 0.50 or less.
It is as follows.

The silver halide color light-sensitive material of the present invention has a good balance with the coated amount of gelatin even though the weight ratio of lipophilic photographic material / gelatin is higher than that of the conventional light-sensitive material. Lipophilic photographic material weight /
An excellent effect is exhibited due to a small difference in gelatin weight ratio.

The photographic constituent layer of the photographic material of the present invention preferably has a calcium content of 50 ppm or less, and particularly preferably 4 ppm or less.
It is preferably at most 0 ppm, more preferably at most 30 ppm. If the calcium content is too high, the film will peel off or devitrify during rapid development, making it impractical.

The calcium in the gelatin forming the photographic constituent layer is derived from the raw materials. To obtain the gelatin having the calcium content of the present invention, the selection of the raw materials, the selection of the production conditions, the ion exchange treatment, etc. May be appropriately combined. As the ion exchange treatment, gelatin may be extracted from raw materials such as beef bone and pig skin, and then subjected to ion exchange using an ion exchange resin (for example, IRA type manufactured by Rohm and Haas Company). The determination of the calcium ion content after the ion exchange treatment may be performed according to the method described in the sixth edition of the photographic gelatin test method (abbreviation: Bagii method) established by the Joint Committee for Gelatin Test Methods.

[0115]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of photosensitive material) A seed crystal emulsion was prepared as follows. JP-B-58-58288, 58-5828
An aqueous solution of silver nitrate (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) were added to the following solution A1 adjusted to 35 ° C. using a mixing stirrer shown in No. 9 While maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV, the mixture was added over 2 minutes by the simultaneous mixing method to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, adjusted to pH 5.0 with an aqueous sodium carbonate solution, and then mixed with an aqueous solution of silver nitrate (5.902 mol) and potassium bromide and potassium iodide. Mixed aqueous solution (potassium iodide 2 mol%)
By the simultaneous mixing method while maintaining the silver potential at 9 mV.
The addition took 2 minutes. After completion of the addition, the temperature was lowered to 40 ° C. and immediately desalted using a normal flocculation method.
Washing was performed.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side ratio of 1.0% or more of 90% or more of the total projected area of silver halide grains.
~ 2.0 hexagonal tabular grains. This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH₂CH₂O) m ｛CH (CH₃) CH₂O｝_19.8(CH₂CH ₂ O) nH (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H₂O 9657ml

Preparation of silver iodide fine grain emulsion SMC-1 While stirring vigorously 5 L of a 6.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide, 7.06 mol
2 liters of an aqueous silver nitrate solution and 2 liters of a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of Emulsion Em-1 0.178 mol of seed crystal emulsion-1 and HO (CH₂CH
₂O) m ｛CH (CH ₃) CH₂O｝_19.8(CH₂
CH₂O) 10% ethanol of nH (m + n = 9.77)
4.5% by weight inert gelatin containing 0.5 ml
700 ml of the aqueous solution at 75 ° C. and pAg of 8.9,
After adjusting the pH to 5.0, mix simultaneously with vigorous stirring.
Particle formation was performed according to the following procedure by a legal method. 1) 2.1 mol of silver nitrate aqueous solution and 0.195 mol of SM
C-1 and an aqueous potassium bromide solution with a pAg of 8.9,
It was added while maintaining the pH at 5.0. 2) Subsequently, a 1.028 mol aqueous silver nitrate solution and 0.03 mol
Two moles of SMC-1 and an aqueous solution of potassium bromide were added to pA
g was maintained at 8.9 and the pH was maintained at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 4 having a side length of 0.65 μm and an average aspect ratio of 7.2. Further, when the surface silver iodide content was measured by the method described in this specification, the surface silver iodide content was 4.5 mol%.

Sensitizing dyes SD-5 and S were added to the above emulsion Em-1.
D-6 and SD-7 were added, and sodium thiosulfate, chloroauric acid, potassium thiocyanate, and selenium sensitizer b were further added.
-1 was added, and chemical sensitization was performed according to a conventional method so as to optimize the fog-sensitivity relationship.

After completion of the chemical sensitization, a stabilizer ST-1 was added to each emulsion.
And an antifoggant AF-1. The amount of ST-1 added was 1 g per mol of silver halide, and the amount of AF-1 was 15 mg per mol of silver halide. As described above, the chemically sensitized emulsion Em-A corresponding to Em-1
Was prepared.

[0125]

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<< Preparation of Multilayer Color Photographic Material Sample >> On a triacetylcellulose film support provided with an undercoat layer, each layer having the following composition was sequentially formed from the support side to prepare a multilayer color photographic material sample 101 Was prepared. In the fifth, tenth and fourteenth layers, the emulsion Em-
A was used. Amount in particular shows the number of grams per 1 m ² unless otherwise noted. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in moles per mole of silver.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling organic solvent (Oil-1) 0.07 Gelatin 1.53

Second layer: Intermediate layer Color stain inhibitor (SC-1) 0.06 High boiling organic solvent (Oil-2) 0.08 Gelatin 0.80

Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 8.0 mol%) 0.45 Silver iodobromide emulsion (average grain size: 0.1%) 27 μm, silver iodide content 2.0 mol%) 0.18 sensitizing dye (SD-1) 2.8 × 10 ⁻⁴ sensitizing dye (SD-2) 1.9 × 10 ⁻⁴ sensitizing dye ( SD-3) 1.9 × 10 ^-4 sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.56 Colored cyan coupler (CC-1) 0.021 DIR compound ( D-1) 0.025 High boiling solvent (Oil-1) 0.49 Gelatin 1.14

Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 0.52 μm, silver iodide content: 8.0 mol%) 0.89 Silver iodobromide emulsion (average grain size: 0.1 mol%) 38 μm, silver iodide content: 8.0 mol%) 0.22 sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye ( SD-3) 1.6 × 10 ^-4 cyan coupler (C-1) 0.45 colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0.017 high boiling point solvent (Oil-1) 0.39 gelatin 1.01

Fifth layer: high-sensitivity red-sensitive layer Emulsion Em-A 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 sensitization Dye-sensitive dye (SD-3) 1.6 × 10 ^-4 cyan coupler (C-2) 0.20 Colored cyan coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High boiling solvent (Oil) -1) 0.37 gelatin 1.10

Sixth layer: Intermediate layer Color stain inhibitor (SC-1) 0.075 High boiling point solvent (Oil-2) 0.095 Gelatin 1.00

Seventh layer: Intermediate layer Gelatin 0.45

Eighth layer: low-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 8.0 mol%) 0.68 Silver iodobromide emulsion (average grain size: 0.1 mol%) 27 μm, silver iodide content 2.0 mol%) 0.18 Sensitizing dye (SD-4) 7.4 × 10 ^-4 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M -1) 0.19 Magenta coupler (M-2) 0.49 Colored magenta coupler (CM-1) 0.12 High boiling solvent (Oil-2) 0.31 Gelatin 1.89

Ninth layer: middle-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size: 0.59 μm, silver iodide content: 8.0 mol%) 0.76 Sensitizing dye (SD-6) 1.5 × 10 ^-4 sensitizing dye (SD-7) 1.6 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-4 magenta coupler (M-1) 0.043 Magenta coupler (M-2) ) 0.10 Colored magenta coupler (CM-2) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.002 High boiling solvent (Oil-2) 0.17 Gelatin 0.76

Tenth layer: high-sensitivity green-sensitive layer Emulsion Em-A 1.46 Magenta coupler (M-1) 0.08 Magenta coupler (M-2) 0.133 Colored magenta coupler (CM-2) 0.014 High boiling solvent (Oil-1) 0.15 High boiling solvent (Oil-2) 0.22 Gelatin 1.08

Eleventh layer: Yellow filter layer Yellow colloidal silver 0.07 Color stain inhibitor (SC-1) 0.18 Formalin scavenger (HS-1) 0.14 High boiling solvent (Oil-2) 0.11 Gelatin 0.73

Twelfth Layer: Intermediate Layer Formalin Scavenger (HS-1) 0.18 Gelatin 0.60

Thirteenth layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average particle size 0.59 μm, silver iodide content 8.0 mol%) 0.075 Silver iodobromide emulsion (average particle size 0. 38 μm, silver iodide content: 3.0 mol%) 0.15 Silver iodobromide emulsion (average grain size: 0.27 μm, silver iodide content: 2.0 mol%) 0.20 Sensitizing dye (SD-9) 2.1 × 10 ⁻⁴ sensitizing dye (SD-10) 2.8 × 10 ⁻⁴ Yellow coupler (Y-1) 0.89 DIR compound (D-4) 0.008 High boiling point solvent (Oil-2) ) 0.27 gelatin 1.51

Fourteenth layer: high-sensitivity blue-sensitive layer Emulsion Em-A 0.95 sensitizing dye (SD-9) 7.3 × 10 ^-4 sensitizing dye (SD-10) 2.8 × 10 ^-4 yellow Coupler (Y-1) 0.16 High boiling point solvent (Oil-2) 0.093 Gelatin 0.80

Fifteenth layer: First protective layer Silver iodobromide emulsion (average particle size: 0.05 μm, silver iodide content: 3.0 mol%) 0.30 UV absorber (UV-1) 0.094 UV Absorbent (UV-2) 0.10 Formalin scavenger (HS-1) 0.38 High boiling solvent (Oil-1) 0.05 Gelatin 1.44

Sixteenth layer: Second protective layer Alkali-soluble matting agent PM-1 (average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.55

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersion aid SU-4, viscosity modifier V-1, stabilizer ST-1, dyes AI-1, AI-2,
Antifoggant AF-1, weight average molecular weight: 10,000
And two kinds of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 100,000, hardeners H-1, H-2 and preservative DI-1 were added. The amount of DI-1 added was 9.4.
mg / m ² . The structure of the compound used in the above sample is shown below.

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(Automatic developing machine) A modified color negative film processor CL-KP-50QA (manufactured by Konica) was used.

[0154]

(Formulation of Processing Solution) Color developer: 1 liter of sodium sulfite 5.0 g potassium carbonate 35.0 g pentasodium diethylenetriaminepentaacetate 4.0 g hydroxylamine sulfate 3.0 g potassium bromide 1.5 g potassium iodide 2 4.0 mg 4-amino-3-methyl-N-ethyl-N (β-hydroxyethyl) aniline sulfate 4.5 g Water was added to make up to 1 liter, and the pH was adjusted to 10 using potassium hydroxide or 50% sulfuric acid. Adjusted to .5.

Bleaching solution: per liter of ferric ammonium 1,3-propylenediaminetetraacetate 133 g sodium 1,3-propylenediaminetetraacetate 5 g ammonium bromide 60 g maleic acid 40 g imidazole 10 g Adjust to pH = 4.3 with water or 20% sulfuric acid.

Fixer per liter: Ammonium thiosulfate 180 g Sodium thiosulfate 20 g Sodium sulfite 18 g Disodium ethylenediaminetetraacetate 2 g Compounds shown in Table 1 (additives) 0.01 mol Silver bromide 0.15 mol Silver iodide 0.008 mol Water And make up to 1 liter, and adjust to pH = 6.5 with aqueous ammonia or 20% sulfuric acid.

Stabilizing solution: per liter m-hydroxybenzaldehyde (Exemplified compound F-2-3) 1.5 g Disodium ethylenediaminetetraacetate 0.6 g β-cyclodextrin 0.2 g Potassium carbonate 0.2 g Finish to liter.

After subjecting the light-sensitive material prepared by the above-described method to wedge exposure by a usual method, an additive (addition amount: 0.01 mol / l) to the fixing solution under the above-mentioned conditions, and processing in the fixing step A processed sample in which the processing is performed as shown in Table 1 by changing the circulation amount of the liquid and the processing temperature, and monovalent silver is left at a ratio as shown in Table 1 below with respect to the coated silver amount before processing. 1 to 21 were created. The additives to the fixing solution for preparing Sample 21 were III-10 and III-23, respectively.
005 mol / l were added.

[0160]

[Table 1]

Samples 1 to 21 were stored in a dark place at 75 ° C. and a relative humidity of 10% RH for 10 days, and the transmission density at 440 nm before and after storage was determined for the portion where the transmission density at 440 nm before storage was 1.0. Was measured (yellow stain concentration). Further, a decrease rate (magenta fading rate) of the transmission density at 550 nm of the maximum density portion after storage was measured. When the magenta fading rate has a negative value, it means that the density has increased. The yellow stain concentration,
The smaller the value of the magenta fading rate is, the more stable it is.
It has good performance. Table 2 shows the results.

[0162]

[Table 2]

As is evident from the results in Table 2, the processing solution contains the compounds represented by the general formulas [I] to [V], and is 1% to 50% by weight of the coated silver halide. When the following silver is present in the light-sensitive material, it is possible to prevent an increase in yellow stain density and to reduce fading of the magenta dye.

Example 2 Rather than subjecting the sensitized material prepared in Example 1 to wedge exposure, it was inserted into photographic equipment and actually photographed to perform processing under the conditions that samples 1 to 21 were prepared. When a printing experiment was conducted in which the material was baked on color negative paper, samples other than the conditions under which samples 1, 2, 15, and 20 were prepared (that is, the remarks column in Example 1 was the one according to the present invention) had no problem at all and were good. It was found that a good print was obtained.

Example 3 An additive was added to a treatment solution at an addition concentration as shown in Table 3,
The same experiment as in Example 1 was conducted, and the yellow stain density was measured in the same manner as in Example 1 except that the darkness storage period was set to 20 days. The amount of circulating fixer and the temperature were adjusted according to the conditions under which Sample 2 of Example 1 was prepared when no additive was used.
In the case of II-10, the test was performed under the conditions under which the sample 6 of Example 1 was prepared. Further, the maximum and minimum transmission densities at 660 nm {Dmax (R), Dmin (R)} were measured for the photosensitive material after processing before storage. The results are summarized in Table 3.
In the table, N1, N2, N3, and N4 indicate a color developing solution, a bleaching solution, a fixing solution, and a stabilizing solution, respectively. The amount added is shown in parentheses next to the compound name. In this embodiment, the larger the value of Dmax (R), the smaller the value of Dmin (R).
The smaller the value of (R), the better the performance.

[0166]

[Table 3]

As is clear from the results in Table 3, the photographic processing solution to which the compound of the present invention is added is a processing solution having a bleaching ability, a processing solution having a fixing ability, or a stabilizing solution. It can be seen that the effects of the present invention can be further exhibited by using a processing solution, or a processing solution having bleaching ability, a processing solution having fixing ability, and a processing solution for stabilization.

Example 4 The light-sensitive material used in Example 1 was processed under the same conditions as in Sample 2 of Example 1 except that the additives were added to the bleaching solution at the addition concentrations shown in Table 4 below. 60 ° C, relative humidity 50
Example 1 except that it was stored in a dark place under the condition of% RH for 10 days.
The yellow stain concentration was measured in the same manner as described above. Also,
At a place where the transmission density at 660 nm before storage was 1.5, the increase in RMS granularity (ΔRMS) was measured before and after storage. RMS granularity is 1800 μm in aperture scanning area
² is 1000 times the standard deviation of the fluctuation of the density value generated when scanning with a microdensitometer having a slit width of 10 μm and a slit length of 180 μm. 3
A relative value of ΔRMS of −1 was 1.00. The smaller the ΔRMS, the better the performance. Further, the treatment liquid in which the addition amount of III-10 was changed was stored in a container having an opening area ratio of 200 cm ² / l under the condition of 50 ° C, and the number of days when the precipitate was confirmed was visually examined.
The results are summarized in Table 4.

[0169]

[Table 4]

As is evident from the results in Table 4, the amount of the compound of the present invention was determined to prevent the increase in yellow stain after storage,
0.0001mo from the viewpoint of prevention of graininess deterioration and precipitation
1 / l to 0.1 mol / l, more preferably 0.005 mol / l to 0.07 mol / l
Is more preferable, and the most preferable range is 0.01 mol / l to 0.05 mol / l.

Example 5 The light-sensitive material used in Example 1 was processed under the same conditions as in Example 1 except that additives were added to the fixing solution at the addition concentrations shown in Table 5 below. 70 ° C, relative humidity 40
Example 1 except that it was stored in a dark place under the condition of% RH for 10 days.
The yellow stain concentration was measured in the same manner as described above. The circulation amount and temperature of the fixing solution were determined in Experiment No. Performed under the same conditions as in 1-6. In a place where the transmission density at 660 nm before storage was 1.5, the RMS granularity before and after storage (ΔRM) was increased.
S) was measured in the same manner as in Example 3. The evaluation of graininess was carried out in Experiment No. The relative values are shown by setting the ΔRMS of 4-1 to 1.00. Further, the treatment liquid in which the addition amount of III-10 was changed was preserved in a vessel having an opening area ratio of 200 cm ² / l under the condition of 50 ° C, and the number of days when the precipitate was confirmed was examined.
The results are summarized in Table 5.

[0172]

[Table 5]

As is evident from the results in Table 5, the amount of the compound of the present invention was determined to prevent the increase in yellow stain after storage,
0.0001mo from the viewpoint of prevention of graininess deterioration and precipitation
1 to 0.1 mol / l, preferably 0.001 mol / l to 0.05 mol / l.
Is more preferable, and the most preferable range is from 0.005 mol / l to 0.03 mol / l.

Example 6 The light-sensitive material used in Example 1 was treated under the same conditions as in Example 1 except that the additives were added to the stabilizer at the additive concentrations shown in Table 6 below. 40 ° C, relative humidity 30
% RH at 70,000 Lux. / H for 7 days. The reduction rate (yellow fading rate) of the transmission density at 440 nm in the maximum density portion of the processed photosensitive material was measured. Further, the fixing solution used when preparing Sample 6 of Example 1 except for silver bromide and silver iodide was added to the stabilizing solution so as to be 10% of the whole, and the addition amount of III-10 was reduced. The changed stable liquid was stored in a vessel having an opening area ratio of 200 cm ² / l under the condition of 50 ° C, and the number of days when the precipitate was confirmed was examined. The results are summarized in Table 6.

[0175]

[Table 6]

As is evident from the results in Table 6, the amount of the compound of the present invention is 0.0001 mol / l to 0.1 mol in view of the discoloration and precipitation of the yellow dye after storage.
/ L, more preferably 0.0005 / l.
mol / l to 0.03 mol / l, more preferably 0.0001 mol / l.
０．０１0.01 mol / l.

Example 7 Emulsions Em-2 to Em-6 used in place of the emulsion Em-1 of the light-sensitive material used in Example 1 were prepared by the following method.

Preparation of Emulsion Em-2 In the preparation of Emulsion Em-1, after the completion of the step 2), the emulsion was dried.
Em-2 was prepared in the same manner as Em-1, except that 004 mol of SMC-1 was added and aged for 16 minutes. The resulting emulsion had a particle size (one side length of a cube of the same volume) of 0.65 μm.
m and an emulsion comprising tabular grains having a halogen composition shown in Table 4 having an average aspect ratio of 7.0. The surface silver iodide content was 12.5 mol%.

Preparation of Emulsion Em-3 0.178 mol of seed crystal emulsion-1 and HO (CH ₂ CH
_{2 O) m {CH (CH} 3) CH 2 O} 19.8 (CH 2
700 ml of a 4.5% by weight aqueous solution of inert gelatin containing 0.5 ml of a 10% ethanol solution of (CH ₂ O) nH (m + n = 9.77) was kept at 75 ° C., and the pAg was 8.9.
After adjusting the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure. 1) 2.1 mol of silver nitrate aqueous solution and 0.195 mol of SM
C-1 and an aqueous potassium bromide solution with a pAg of 8.9,
It was added while maintaining the pH at 5.0. 2) Subsequently, the temperature of the solution was lowered to 60 ° C., and the pAg was adjusted to 9.8. Thereafter, 0.071 mol of SMC-1 was added and aging was performed for 2 minutes (introduction of dislocation lines). 3) pAg of 0.959 mol of silver nitrate aqueous solution, 0.030 mol of SMC-1 and potassium bromide aqueous solution was adjusted to 9.
8. It was added while maintaining the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and gelatin was added to redisperse the mixture. The pAg was adjusted to 8.1 and the pH was adjusted to 5.5.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 4 having a side length of 0.65 μm and an average aspect ratio of 7.2. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.3 mol%.

Preparation of Emulsion Em-4 Em-3 was prepared except that the amount of silver nitrate added in step 2) was 0.91 mol and the amount of SMC-1 was 0.069 mol in the preparation of emulsion Em-3. Emulsion Em-4 was prepared in the same manner as described above.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was composed of tabular grains having a halogen composition shown in Table 4 having a side length of 0.65 μm and an average aspect ratio of 6.5. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.5 mol%.

Preparation of Emulsion Em-5 0.178 mol of seed crystal emulsion-1 and polyisoprene
4.5% by weight containing 0.5 ml of a 10% ethanol solution of polyethylene oxydisuccinate sodium salt
Of inert gelatin aqueous solution at 75 ° C.
After adjusting the Ag to 8.9 and the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure. 1) A pAg of a 0.692 mol silver nitrate aqueous solution, 0.297 mol SMC-1 and potassium bromide aqueous solution was set to 8.
9. Added while keeping the pH at 5.0. 2) Subsequently, a 2.295 mol silver nitrate aqueous solution and 0.07 mol
1 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g was maintained at 8.9 and the pH was maintained at 5.0. 3) After the step 2), 0.004 mol of SMC-1
Was added and aged for 15 minutes.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After the above step 3), after performing a water washing treatment at 40 ° C. using a normal flocculation method,
Gelatin was added for redispersion, and the pAg was adjusted to 8.1 and the pH was adjusted to 6.0.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 4 having a side length of 0.65 μm and an average aspect ratio of 4.1. Observation of this emulsion with an electron microscope revealed that there were no grains having dislocation lines. The surface silver iodide content is 1
1.7 mol%.

Preparation of Emulsion Em-6 The Em- described in Example of JP-A-7-92594 was used.
In accordance with the production method of Comparative Example 4, Comparative Emulsion Em-6 was prepared.

The emulsions Em-2 to Em-2 prepared as described above
Table 7 shows the content of Em-6, including Em-1 produced in Example 1.

[0189]

[Table 7] 1) The silver iodide content (mol%) of each phase is shown. X indicates a dislocation line introduction position. 2) Aspect ratio at 50% of the total projected area of silver halide grains in each emulsion. 3) → indicates that the iodine composition was continuously changed in the formulation.

Sensitizing dyes SD-5, SD-6 and SD-7 were added to the above emulsions Em-2 to Em-6, and sodium thiosulfate, chloroauric acid, potassium thiocyanate and selenium sensitizer b were added. -1 was added, and chemical sensitization was performed according to a conventional method so as to optimize the fog-sensitivity relationship.

After completion of the chemical sensitization, a stabilizer ST-1 was added to each emulsion.
And an antifoggant AF-1. The amount of ST-1 was 1 g per mol of silver halide, and the amount of AF-1 was 15 mg per mol of silver halide. As described above, chemically sensitized emulsion E corresponding to Em-2 to Em-6
m-B to Em-F were prepared.

The fifth and first samples 101 of the sample 101 used in the first embodiment
Samples 102 to 106 were prepared by replacing the emulsion Em-A of the 0th and 14th layers with the emulsions Em-BF. The sample prepared as described below was processed with the fixing solution and the processing conditions for preparing sample 6 of Example 1, and the processed photographic material was subjected to 70,000 Lux. / H for 10 days. 440 of the maximum density part of the photosensitive material after processing
The decrease rates of the transmission densities at 550 nm and 550 nm (yellow fading rate and magenta fading rate, respectively) were measured. Table 8 shows the results.

[0193]

[Table 8]

From the results shown in Table 8, it was found that the silver halide photographic light-sensitive material had an aspect ratio of 5 or more in 50% or more of the total projected area.
A tabular silver halide having a thickness of 0.1 μm or more and 0.3 μm or less, wherein 50% or more of the tabular silver halide has a maximum silver iodide content of less than 15 mol% of the phase excluding the outermost layer. The effect of the present invention is further enhanced by containing at least one silver halide emulsion having a silver iodide content of the outermost layer of 6 mol% or more and having 5 or more dislocation lines per grain. It is clear that it can be used.

Example 8 In place of m-hydroxybenzaldehyde (exemplified compound F-2-3) in the stabilizer used in Example 1, an equimolar amount of a compound shown in Table 9 was added. II
The light-sensitive material used in Example 1 was processed under the conditions in which Sample 2 of Example 1 was prepared, using a stabilizer to which I-10 was added in the amount shown in Table 9. After the processing, the photosensitive material was subjected to 75000 Lux. / H for 10 days. 55 of the maximum density part of the photosensitive material after processing
The decrease rate of the transmission density at 0 nm (magenta fading rate) was measured. Table 9 shows the results.

[0196]

[Table 9]

As is clear from Table 9, the effects of the present invention can be further exerted when the stabilizer contains at least one compound represented by any one of the above formulas (F-1) to (F-3). You can see that

[0198] In replenishment of the photosensitive material 1 m ² per 550ml to be processed using the fixing replenisher, as shown in Example 9 below, and the compounds of the present invention in the III-10, Experiment No. Using the conditions of 1-6, the photosensitive material used in Example 1 was continuously processed at a processing amount of 1.2 m ² per day for one month. This continuous processing is referred to as continuous processing 1.

Fixing replenisher: 1 liter per liter of ammonium thiosulfate 144 g sodium thiosulfate 16 g sodium sulfite 18 g disodium ethylenediaminetetraacetate 2 g Compound of the present invention III-10 0.01 mol The pH is adjusted to 6.5 using% sulfuric acid.

In the above-described continuous processing 1, the stable processing tank 3
From the stabilizing tank closest to the fixing tank of the tank, 275 ml per 1 m ^{2 of the} photosensitive material is supplied to the immediately preceding fixing processing tank in the second tank by a bellows pump, so that the above-mentioned fixing replenisher is concentrated twice to make the photosensitive material 1 m ² A continuous processing experiment was performed by replenishing 275 ml per second in the second fixing processing tank. This is referred to as continuous processing 2. After each continuous treatment, the photographic material used in Example 1 was processed, and the photosensitive material was treated at 75 ° C. and a relative humidity of 10% RH.
It was stored in a dark place for 0 days, and the decrease rate (magenta fading rate in a dark place) of the 550 nm transmission density of the maximum density portion after storage was measured. 70,000 L at 40 ° C and 20% RH
ux. / H for 10 days. The rate of decrease in the transmission density at 550 nm in the maximum density portion of the processed photosensitive material (light magenta fading rate) was measured. Table 10 shows the results.

[0201]

[Table 10]

From the results shown in Table 10, the effects of the present invention can be further exhibited by directly introducing the processing solution for stabilization into the processing tank before the step of processing using the processing solution for stabilization. At the same time, the total waste liquid amount can be reduced to about 90%.

Example 10 In the sample 101 of Example 1, the high boiling solvent O
The amounts of il-1 and il-2 were increased at the same ratio, and the ratio of total lipophilic photographic material weight / total gelatin weight (O / G) in the photosensitive material was increased.
The ratio was as shown in Table 11 below, and the photosensitive material was adjusted such that the total gelatin coating amount was as shown in Table 11 below. The yellow stain density was measured in the same manner as in Example 1 except that the processing was performed under the conditions, and the processed photosensitive material was stored in a dark place at 70 ° C. and a relative humidity of 40% RH for 15 days. The circulation amount and temperature of the fixing solution were determined in Experiment No. Performed under the same conditions as in 1-6. Further, at a place where the transmission density at 660 nm before storage was 1.2, the numerical value (ΔRMS) of the increase in RMS granularity before and after storage was measured in the same manner as in Example 3. The evaluation of graininess was carried out in Experiment No. The relative value of ΔRMS of 9-1 was 1.00. The results are shown in Table 11. In addition, the sample No. The composition was 9-8.

[0204]

[Table 11]

As is clear from the results shown in Table 11, the weight ratio of the total lipophilic photographic material / the total weight of the gelatin in the silver halide photographic light-sensitive material is 0.50 or more and 0.70 or less, and the total gelatin coating amount is small. 14.0 g / m ² or more and 18.0 g / m
It is understood that the effect of the present invention can be further exhibited when the ratio is ² or less.

Example 11 Sample 101 of Example 1 was replaced with gelatin having a different calcium content so as to adjust the calcium content of all the constituent layers of the light-sensitive material as shown in Table 12 below.
These photographic materials were processed under the fixing solution and processing conditions for preparing Sample 6 of Example 1, and the processed photographic materials were stored in a dark place at 70 ° C. and 40% RH for 15 days. The yellow stain concentration was measured in the same manner as in Example 1.
The circulation amount and temperature of the fixing solution were determined in Experiment No. Performed under the same conditions as in 1-6. The transmission density at 660 nm before storage is 0.8
, The increase in RMS granularity before and after storage (Δ
RMS) was measured as in Example 3. Note that ΔRMS
The values of Experiment No. The relative values are shown by setting the ΔRMS value of 10-1 to 1.00. The results are shown in Table 12. Sample 1
The calcium content of 01 was 30 ppm.

[0207]

[Table 12]

It can be seen that the effects of the present invention can be further exhibited when the calcium content in the silver halide photographic material is 50 ppm or less and 5 ppm or more.

Example 12 Experiment No. 9 of Example 9 was performed. In 8-1, the same continuous processing was performed except that the replenishing amount of the fixing solution was changed as shown in Table 13 below, and the concentrations of III-10 in the fixing solution and the fixing replenishing solution were changed. After each continuous processing, the photographic material used in Example 1 was processed and stored in a dark place at 75 ° C. and a relative humidity of 10% RH for 20 days, and stored in a place where the transmission density at 440 nm was 1.3 before storage. The difference between the transmission density before and after 440 nm (yellow stain density) was measured, and the decrease rate (magenta fading rate in a dark place) of the maximum 550 nm transmission density after storage was measured. The results are shown in Table 13.

[0210]

[Table 13]

As is clear from the results shown in Table 13, the effects of the present invention can be further exhibited when the replenishment rate of the fixing solution is 900 ml / m ² or less and 100 ml / m ² or more.

Example 13 Experiment No. 9 of Example 9 In 8-1, the molar ratio of thiosulfate ion was kept constant, and the ratio of ammonium thiosulfate and sodium thiosulfate was adjusted. As shown in Table 14 below, ammonium ion (NH _{4 ⁺⁾} by changing the ratio of, was subjected to the same continuous process except for changing the concentration of III-10 of the fixing solution and fixing replenisher. After each continuous treatment, the photographic material used in Example 1 was processed, and the relative humidity was 30% at 60 ° C.
Store in the dark for 15 days under RH conditions, 440n before storage
The difference of the transmission density at 440 nm (yellow stain density) before and after storage at a place where the transmission density of m is 1.3 (yellow stain density) was measured, and the reduction rate of the transmission density at 550 nm of the maximum density portion after storage (magenta fading rate in a dark place) was measured. Was measured. The results are shown in Table 14.

[0213]

[Table 14]

As is clear from the results in Table 14, the ratio of ammonium ion to all cations in the fixing solution was 0%.
% And 50 mol% or less, it can be seen that the effects of the present invention can be more fully exhibited. Further, the ratio of ammonium ions to all cations is 50 mol%.
It was found that the odor of the fixing solution was reduced by the following.

Example 14 Experiment No. 1 of Example 1 In 1-6, the circulation ratio of the fixing processing tank was changed as shown in Table 15 below, and
-10 was changed as shown in Table 15, and the concentrations of silver bromide and silver iodide in the fixing solution were each 0 mol / mol.
The same processing experiment was performed except that the liter was used.

Using a Konica Color JX400 (manufactured by Konica Corporation) which has been subjected to ordinary wedge exposure as a photosensitive material, the processed sample was treated at 10 ° C. under the conditions of 60 ° C. and 50% relative humidity RH.
The sample was stored in a dark place for one day, and the difference in the transmission density at 440 nm (yellow stain density) before and after storage in a place where the transmission density at 440 nm before storage was 1.3 was measured.
The rate of decrease in the transmission density of 0 nm after storage (magenta fading rate in a dark place) was measured. The results are shown in Table 15.

[0219]

[Table 15]

As is clear from the results shown in Table 15, the circulation ratio of the fixing processing tank was from 0.2 round / min to 0.8 r.
It can be seen that the effect of the present invention can be further exhibited when the ratio is in the range of sound / min. It was also found that when the circulation ratio was 0.8 round / min or less, the storage stability of the fixing solution was improved.

Example 15 The silver iodide content of the emulsion Em-1 prepared in Example 1 was adjusted to change the silver iodide ratio of the whole light-sensitive material as shown in Table 16 below. A light-sensitive material in which the amount of silver was changed as shown in Table 8 was prepared. The size of the silver halide grains was appropriately adjusted in order to maintain the gradation.

Table 1 shows the concentration of the compound III-10 of the present invention.
6, except that it was changed as shown in FIG.
o. The same processing as in 1-6 is performed on each photosensitive material.
The sample after the treatment was treated under the conditions of 60 ° C. and 40% RH for 2 hours.
It was stored in a dark place for 0 days, and the decrease rate (magenta fading rate in a dark place) of the 550 nm transmission density of the maximum density portion after storage was measured.

Further, for each sample after storage, the granularity (RMS value) was evaluated at a place where the transmission density at 440 nm was 1.8 in the same manner as in Example 4. 15-1
Was expressed as a relative value with the RMS value of 1.00 being 1.00. Note that R
The smaller the MS value, the better the performance. The results are shown in Table 16.

[0222]

[Table 16]

As is clear from Table 16, the silver iodide content of the silver halide in the light-sensitive material was 0.5 mol% to 10 mol%.
in the range of mol%, or by silver halide light-sensitive material is applied in 2000 mg / ^{m 2} or more 7000 mg / ^{m 2} or less of the range, the effect of the present invention more apparent that more can be exhibited.

Example 16 A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material. The coating solution was adjusted as described below.

Coating solution for first layer Yellow coupler (PY-1) 23.4 g, dye image stabilizer (PST-1) 3.34 g, (PST-2) 3.
34 g, 3.34 g of (PST-5), 0.34 g of stain inhibitor (PHQ-1), 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (PDBP) and high-boiling organic solvent (PDNP) 60 ml of ethyl acetate was added to and dissolved in 67 g, and this solution was dissolved in 20% surfactant (PSU-1) 7.
The mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution. Each coating solution for the second layer to the seventh layer was prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 1 and 2. (PH-1) and (PH-2) were added as hardeners. Surfactants (PSU-
1) was added to adjust the surface tension. PF-
1 was added so that the total amount was 0.04 g / m ² .

[0226]

[Table 17]

[0227]

[Table 18]

PSU-1: sodium tri-i-propylnaphthalenesulfonate PDBP: dibutyl phthalate PDNP: dinonyl phthalate PDOP: dioctyl phthalate PDIDP: di-i-decyl phthalate PPVP: polyvinylpyrrolidone PH-1: teratokis (vinylsulfonylmethyl) )
Methane PH-2: 2,4-dichloro-6-hydroxy-s
-Triazine sodium PHQ-1: 2,5-di-t-octylhydroquinone PHQ-2: 2,5-di-sec-dodecylhydroquinone PHQ-3: 2,5-di-sec-tetradecylhydroquinone PHQ-4 : 2-sec-dodecyl-5-sec-tetradecylhydroquinone PHQ-5: 2,5-di [(1,1-dimethyl-4-
Hexyloxycarbonyl) butyl] hydroquinone Image stabilizer A: Pt-octylphenol

[0229]

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[0230]

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[0231]

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[0232]

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[0233]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

[0235] (A solution) Sodium chloride 3.42g Potassium bromide 0.03g Water to make 200 ml (B solution) was added silver nitrate 10g water 200 ml (C solution) Sodium chloride 102.7g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol _{Ag K 4 Fe (CN) 6} 2 × 10 -5 mol / mol Ag potassium bromide 1.0g water to make 600ml (D solution) Silver nitrate 300g water to make 600ml

After completion of the addition, Demol N manufactured by Kao Atlas Co., Ltd.
And a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm, a variation coefficient of particle size distribution of 0.07, and a silver chloride content of 99. A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the average particle size was 0.66 μm, and the particle size distribution was the same as in EMP-1 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. And a monodisperse cubic emulsion EMP-1B having a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver amount of 1: 1 to obtain a blue-sensitive silver halide emulsion (PEm-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX stabilizer PSTAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer PSTAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent PSTAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye PBS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye PBS-2 1 × 10 ⁻⁴ mol / mol AgX

(Preparation of Green-Sensitive Silver Halide Emulsion)
Liquid) and (solution B) and the addition time of (liquid C) and (liquid D) in the same manner as EMP-1, except that the addition time was changed, the average particle diameter was 0.40 μm, the coefficient of variation was 0.08, and the silver chloride was changed. Content 9
A 9.5% monodisperse cubic emulsion EMP-2 was obtained. next,
A monodisperse cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (PEm-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX stabilizer PSTAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer PSTAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent PSTAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye PGS-1 4 × 10 ⁻⁴ mol / mol AgX

(Preparation of Red-Sensitive Silver Halide Emulsion)
Liquid) and (solution B) and the addition time of (liquid C) and (liquid D) in the same manner as EMP-1, except that the addition time was changed, the average particle diameter was 0.40 μm, the coefficient of variation was 0.08, and the silver chloride was changed. Content 9
A 9.5% monodisperse cubic emulsion EMP-3 was obtained. A monodispersed cubic emulsion EMP-3B having an average particle size of 0.38 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (PEm-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer PSTAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer PSTAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent PSTAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye PRS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye PRS-2 1 × 10 ⁻⁴ mol / mol AgX PSTAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole PSTAB-2: 1-phenyl-5-mercaptotetrazole PSTAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole -1 was added in an amount of 2.0 × 10 ⁻³ per mol of silver halide.

[0245]

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[0246]

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When adjusting the above-mentioned silver halide emulsion,
By appropriately adjusting the amounts of sodium chloride and potassium bromide in Solution A, photosensitive materials having silver chloride contents as shown in Table 19 were prepared. Also, PEm-B, P in Tables 17 and 18
Photosensitive materials as shown in Table 19 were prepared by changing the amounts of Em-G and PEm-R. The light-sensitive material prepared by the above method has a silver chloride content of 99.5% and a coated silver amount of 560 mg.
/ M ² . Each photosensitive material was cut to a width of 35 mm, subjected to wedge-shaped exposure by a usual method, and increased the transport speed of CL-KP-50QA used in Example 1 to 8.86 times under the following conditions. Processing was carried out using a modified version.

[0248]

(Formulation of processing solution: per liter) [Color developing solution] Sodium sulfite 0.10 g Diethylenetriaminepentaacetic acid pentasodium 3.0 g Polyethylene glycol having a weight average molecular weight of 4000 10.0 g Bis (sulfoethyl) hydroxylamine disodium 4 1.0 g Tinopearl SFP [manufactured by Ciba Geigy] 1.0 g sodium p-toluenesulfonate 30.0 g mannitol 6.0 g potassium chloride 4.0 g pine flow 3.0 g Color developing agent 3-methyl-4-amino-N-ethyl -N- (β-methanesulfonamidoethyl) -aniline sulfate [CD-3] 7.5 g Potassium carbonate 33.0 g Lithium hydroxide 3.5 g N-myristoylalanine sodium 0.3 g Add water to make 1 liter, Potassium hydroxide or sulfuric acid 10 pH using. Adjusted to zero.

[Bleach] [0250] Ferric ammonium 1,3-propylenediaminetetraacetate 70 g 1,3-Propylenediaminetetraacetate 5 g Ammonium bromide 60 g Maleic acid 40 g Add water to make 1 liter, and add ammonia water or 20% Adjust to pH 4.0 with sulfuric acid.

[Fixing solution] Ammonium thiosulfate 60 g Sodium thiosulfate 10 g Sodium sulfite 18 g Disodium ethylenediaminetetraacetate 2 g Compound of the present invention (III-10) listed in Table 20 0.09 mol of silver chloride PH is adjusted to 6.5 using ammonia water or 20% sulfuric acid.

[Stabilizing Solution] 1-hydroxyethylidene-1,1-diphosphonic acid trisodium 3.0 g ethylenediaminetetraacetic acid disodium 1.5 g sodium carbonate 0.5 g o-phenylphenol 0.08 g using sodium carbonate or sulfuric acid The pH was adjusted to 8.0.

After processing, each photosensitive material was heated at 40 ° C. 30
% RH at 70,000 Lux. / H for 10 days. 440 nm of the maximum density part of the photosensitive material after processing
And the reduction rate of the reflection density at 550 nm (yellow fading rate and magenta fading rate, respectively) were measured. The results are summarized in Table 19. In addition, the remaining silver was determined by an ordinary X-ray fluorescence method.

[0254]

[Table 19]

As is apparent from Table 19, the silver halide content of the light-sensitive material is 80 mol% or more, or the light-sensitive material contains 200 mg / m 2 of silver halide.
By being applied in the range of ² or more 700 mg / m ² or less, it is clear that it becomes possible to realize good image storability in rapid processing of color paper.

[0256]

According to the present invention, even when 1% by weight or more and 50% by weight or less of silver halide remaining in the light-sensitive material is coated on the light-sensitive material, the image-preserving property of the image forming portion is excellent. Further, it is possible to obtain a good print without any influence on the transmitted light.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/74 G03C 1/74 7/44 7/44

Claims (14)

[Claims] 1. A silver halide color photographic light-sensitive material is processed with a processing solution containing at least one compound represented by the following general formulas [I] to [V], and the halogenation of the light-sensitive material before processing is performed. An image forming method for a silver halide color photographic light-sensitive material, wherein 1% by weight or more and 50% by weight or less of silver amount is left as a silver salt in a processed silver halide color photographic light-sensitive material. Embedded image [In the formula, Q represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring (including a condensed 5- to 6-membered unsaturated ring), and R ₁ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 6 alkyl groups, cycloalkyl groups, aryl groups, heterocyclic groups (5 to
A 6-membered unsaturated ring is condensed) or an amino group. ] [Wherein, R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. Represent. A is-(C = X) -N (R)
_{(R '), - (CH} 2) n 2 - (C = X) -N (R)
_{(R '), - (S} ) m 1 - (C = X) -N (R)
_{(R '), - (S} ) m 2 - (CH 2) n 3 - (C = X)
-N (R) (R ') , - (S) m 3 - (CH 2) n 4 -
N (R) (R ') , - (S) m 4 -N (R) (R'),
_{- (NH) n 5 - (} CH 2) m 5 - (NH) n 6 - (C
= X) -N (R) (R '), -SS- (C = X) -N
(R) (R '), - SZ or _{n 1} valent heterocyclic residue (5
To 6-membered unsaturated rings).
Here, R and R ′ have the same meanings as R ₂ and R ₃ , respectively, and X
Represents ＳS, ＯO, or ＮＲNR ″, and Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl group, or —S—B—Y (R ₄ )
(R ₅ ), wherein R ″ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (some having a condensed 5- to 6-membered unsaturated ring may be used) Including)
Or n represents an amino group, and n _{1 to} n ₆ and m _{1 to} m ₅ each represent an integer of 1 to 6. B represents the number 1-6 alkylene group with a carbon, Y is -N <, = C <or represents -CH <, _{R 4} and _{R 5} have the same meanings as _{R 2} and _{R 3,} respectively. However _{R 4} and _{R 5} may each represent -B-SZ, also _{R 2} and _R 3, R and R ', _{R 4} and _{R 5} may be bonded to each other to form a ring. ] [In the formula, Q ₁ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring (including a condensed 5- to 6-membered unsaturated ring), and R ₁₁ ′ represents a hydrogen atom, an alkali metal atom. , Or an alkyl group. However, Q 'has the same meaning as that of _{Q 1.} ] [In the formula, n ₂ , n ₃ , and n ₄ represent integers of 0 to 5. X represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an acyl group.
M represents a hydrogen atom or an alkali metal. R ₂₁ has 1 carbon atom
And represents a substituted or unsubstituted alkyl group or hydrogen atom.
In addition, the disulfide dimer of this compound is also included. ] [In the formula, Z ₁ and Z ₂ represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an amino group, a carboxyl group, a sulfonic acid group, or a hydroxyl group. _{n 5, n 6, n 7} , n 8, n 9 is an integer of 0-5. ] 2. A silver halide color according to claim 1, wherein said processing solution is at least one selected from a processing solution having a bleaching ability, a processing solution having a fixing ability, and a processing solution for stabilization. An image forming method for a photographic light-sensitive material. 3. The method for forming an image on a silver halide color photographic material according to claim 2, wherein said processing solution is a bleaching solution and / or a fixing solution. 4. The method according to claim 1, wherein the content of the compound represented by the general formulas [I] to [V] in the treatment solution is 0.0001 mol / L or more and 0.1 mol / L. An image forming method of the silver halide color photographic light-sensitive material according to any one of the above. 5. The processing solution according to claim 1, wherein the processing solution is a fixing solution, and the replenishing amount of the fixing solution is 900 ml or less and 100 ml or more per 1 m ^{2 of the} photosensitive material to be processed. An image forming method for a silver halide color photographic light-sensitive material. 6. The processing solution is a fixing solution, wherein the ratio of ammonium ions to all cations in the fixing solution is 0%.
5. The method for forming an image of a silver halide color photographic light-sensitive material according to claim 1, wherein the content is 50 mol% or less. 7. The processing solution is a fixing solution, wherein the volume of the fixing processing tank is A liter, and the circulation amount of the fixing solution is B liter / m
and the circulation ratio B / A of the fixing treatment tank is 0.2 to 0.2
5. The method for forming an image on a silver halide color photographic material according to claim 1, wherein the ratio is 0.8. 8. The method according to claim 1, wherein the silver halide color photographic light-sensitive material is
The halogen according to any one of claims 1 to 7, wherein at least one layer contains a silver halide emulsion having tabular silver halide grains having an aspect ratio of 5 or more in at least 50% of the total projected area. An image forming method for a silver halide color photographic light-sensitive material. 9. The lipophilic photographic material weight / total gelatin weight ratio in the silver halide color photographic light-sensitive material is 0.50 to 0.50.
0.70 and the total gelatin coating weight was 14.0 g /
The image forming method of a silver halide color photographic light-sensitive material according to any one of claims 1-7, characterized in that m is ² or more 18.0 g / m ² or less. 10. The image of a silver halide color photographic light-sensitive material according to claim 1, wherein the calcium content in said silver halide color photographic light-sensitive material is 5 ppm or more and 50 ppm or less. Forming method. 11. The silver halide emulsion according to claim 1, wherein at least one layer of the silver halide emulsion in the silver halide color photographic light-sensitive material has a silver chloride content of 80 mol% or more, including 100%. An image forming method of the silver halide color photographic light-sensitive material according to any one of the above. 12. The image formation of a silver halide color photographic light-sensitive material according to claim 11, wherein the coating amount of silver halide in said silver halide color photographic light-sensitive material is 200 to 700 mg / m ^2. Method. 13. The silver halide emulsion according to claim 1, wherein at least one layer of the silver halide emulsion in the silver halide color photographic light-sensitive material has a silver iodide content of 0.5 to 10 mol%.
11. The method for forming an image of a silver halide color photographic light-sensitive material according to any one of the above items 10. 14. The image formation of a silver halide color photographic light-sensitive material according to claim 13, wherein the coating amount of silver halide in said silver halide color photographic light-sensitive material is ² to 7 g / m ^2. Method.