JPH1090841A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To rapidly obtain an ultrahigh contrast negative image by processing a silver halide photographic sensitive material containing a specified hydrazine derivative with a development processing solution containing a specified aminophenol derivative. SOLUTION: The silver halide photographic sensitive material containing the hydrazine derivative represented by formula I; A-(B)m is processed with the development processing solution containing the aminophenol derivative represented by formula III and the like. In formula I, A is a bonding group; B is a group represented by formula II; and (m) is an integer of 2-6, and in formula II, each of Ar1 and Ar2 is an aromatic or aromatic heterocyclic group; each of L1 and L2 is a bonding group; (n) is 0 or 1; R10 is an H atom or a blocking group; G1 is a -CO or -COCO- group or the like; and each of A10 and A20 is an H atom or one of both is an H atom and the other is an optionally substituted alkylsulfonyl group or the like, and in formula III, each of R1 -R4 is an H atom or a substituent; and each of R5 and R6 is an alkyl or alkenyl group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material containing a hydrazine derivative with a developer having a low environmental load to quickly form an image having ultra-high contrast photographic characteristics. is there.

[0002]

2. Description of the Related Art Silver halide photographic materials are used in the field of plate making,
It is used in a wide range of fields such as the field of medical diagnosis. As the fields of use have been expanded and deepened, the demand for development processing steps required for image formation has increased. In particular, rapid and stable development processing has been strongly desired.

After exposure, a silver halide photographic light-sensitive material is generally processed in the steps of developing, fixing and washing with water. Above all, the black-and-white developer uses hydroquinone, which is a dihydroxybenzene-based compound, as a developing agent, aminophenols or 3-quinone.
Pyrazolidones are used as auxiliary developing agents, and alkaline solutions including sulfites are generally used, but it is also known that enediols such as ascorbic acid function in addition to dihydroxybenzene compounds as developing agents.
It is attracting attention as a developing agent having no ecological or toxicological problems. For example, US Pat. No. 2,688,
Nos. 549 and 3,826, 654 describe that ascorbic acid is used as a developing agent and that an image can be formed under a highly alkaline condition of at least pH 12 or more.
However, these image forming methods are not satisfactory in terms of speed and in obtaining a high-contrast image.

Some attempts have been made to increase contrast in development systems using ascorbic acid. For example, Zwicky states that when ascorbic acid is used as the only developing agent, a kind of squirrel effect appears (J. Phot. Sc. 27, 185 (1979)). It was a system with much lower contrast than. In U.S. Pat. No. 3,022,168, ascorbic acid developing agent, N-methyl-p-aminophenol is used as an auxiliary developing agent, and high-contrast image formation can be performed under a relatively low pH of 8 to 9. It is possible. However, these image forming methods are not satisfactory in terms of speed, and a large amount of boric acid needs to be contained in the developer, which is not preferable from the viewpoint of the environment. Further, Japanese Patent Publication No. 49-46939 and U.S. Pat. No. 5,474,879 disclose a system in which a bisquaternary ammonium salt and ascorbic acid are used in combination. Almost not seen. JP-A-4-32838 also describes the effect of using a quaternary salt in a system using ascorbic acid as a developing agent and p-aminophenols or N-alkyl-p-aminophenols as an auxiliary developing agent. However, the contrast of the obtained image is not sufficient, and there is no mention of improvement in development progress. Further, Japanese Unexamined Patent Publication No.
No. 88306 discloses that high contrast can be obtained by using ascorbic acid as the sole developing agent and maintaining the pH at 12.0 or higher. However, such a developing solution is significantly deteriorated by air oxidation and has a great effect on the stability of the developing solution. There's a problem. There is also an example in which a special developing solution containing ascorbic acid and a hydrazine derivative as main components can be used to form a developing system having high sensitivity and low stain and fog (US Pat. No. 3,730,727). No mention is made of improving the contrast.

It is known to process hydrazine-containing light-sensitive materials with an ascorbic acid developer solution, as disclosed in US Pat.
No. 6, WO93 / 11456, etc.,
Neither is sufficient in both contrast and quickness,
In the latter case, the amine is contained in the developer to make the contrast high, but it is environmentally unfavorable. From the viewpoint of toxicology, there is a demand for a developing method for obtaining a high-speed and high-contrast image by using ascorbic acid, which is preferable as a developing agent, but does not provide sufficient contrast.

On the other hand, in the field of graphic arts, in order to improve the reproduction of continuous-tone images or the reproduction of line images by halftone images, ultra-high contrast (particularly, when γ is 10
An image forming system exhibiting the above photographic characteristics is required. There has been a demand for an image forming system which can be developed with a processing solution having good storage stability to obtain ultra-high contrast photographic characteristics. One of them is U.S. Pat. Nos. 4,166,742 and 4,1.
68,977, 4,221,857, 4,22
4,401, 4,243,739, 4,27
As can be seen in JP-A Nos. 2,606 and 4,311,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound has been added is used.
A system has been proposed which forms a negative image having a super-high contrast of more than 10 by processing with a developer having a pH of 11.0 to 12.3 containing 5 mol / l or more. This new image forming system can use only silver chlorobromide having a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver chloroiodobromide. There is. Another characteristic is that the conventional squirrel developer can contain only a trace amount of the sulfite preservative, whereas it can contain a large amount of the sulfite preservative, so that the storage stability is relatively good. . However, a developer having a pH of 11 or more is easily oxidized by air, is unstable, and cannot withstand long-term storage or use. There have been attempts to develop a silver halide photosensitive material containing a hydrazine compound with a developer having a lower pH to form a high contrast image. JP-A-1-179939 and JP-A-1-179940 disclose a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a sensitizer containing a nucleator having the same adsorptive group. And a processing method for developing with a developer having a pH of 11.0 or less. However, the emulsions used in these inventions are:
These are silver bromide and silver iodobromide emulsions, and the photographic performance greatly changes with the progress of development or the composition of the processing solution, and the stability is not sufficient.

US Pat. Nos. 4,998,604,
994,365 and 4,975,354 disclose a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, according to the description of the examples, in these inventions, high contrast is not enough, and it is difficult to obtain high contrast and necessary Dmax under practical development conditions. Further, the nucleation-sensitive material using a hydrazine derivative has a large change in photographic properties due to a change in pH of the developer. The pH of the developing solution fluctuates greatly due to an increase due to air oxidation of the developing solution and concentration due to evaporation of water, or a decrease due to absorption of carbon dioxide in the air. Accordingly, attempts have been made to reduce the dependence of photographic performance on the developer pH.

By the way, returned light-sensitive materials generally handled in a light room have a large field as one of the light-sensitive materials for plate making. In this field, there is a demand for high blank character quality that reproduces thin Mincho characters. Therefore, development of a nucleating agent having higher activity has been desired. In particular, in a light-sensitive material having a low sensitivity that can be handled in a light room, hardening by a nucleating agent hardly occurs, and development of a nucleating agent having higher activity is desired.

In order to achieve such an object, for example, JP-A-6-148828, JP-A-6-180477
And a highly active hydrazine nucleating agent disclosed in JP-A-6-194774 and the like. In particular, a nucleating agent having, as an acyl group, a substituted alkyl group substituted with at least one electron-withdrawing group can obtain extremely hard photographic properties even in a developing solution having a pH of 11 or less, and can provide photographic performance due to fatigue of the developing solution. However, the nucleating agent itself was easily oxidized, and some of them required improvement in terms of storage stability.

[0010]

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a hydrazine derivative having a specific structure by using a stable developing solution containing an ascorbic acid derivative and a specific aminophenol derivative. It is an object of the present invention to provide a novel image forming method capable of giving a rapid and ultra-high contrast negative image by developing.

[0011]

These objects of the present invention have been attained by the following constitutions. 1) A silver halide photographic material containing a hydrazine derivative represented by the following general formula (1) contains at least one aminophenol derivative represented by the general formula (I) or (II) An image forming method characterized by processing with a developing solution. General formula (1) A- (B) _{m In the} formula, A represents a linking group, B represents a group represented by the following general formula (2), and m represents an integer of 2 to 6. The groups represented by a plurality of Bs linked to A may be the same or different.

[0012]

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In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁₀ represents a hydrogen atom or a block group, G ₁ is -CO -, - COCO -, - C (= S)
—, —SO ₂ —, —SO—, —PO (R ₃₀ ) — group (R ₃₀
It is selected from the same range as the groups defined in R _10, may be different from R _10. ), A thiocarbonyl group, or an iminomethylene group. A ₁₀ and A ₂₀ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

[0014]

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In the general formulas (I) and (II), R ₁ , R ₂ , R ₃ , R ₄ , R ₁₁ , R ₂₂ , R ₃₃ and R ₇₇ may be the same or different. , Each represents a hydrogen atom or a substituent. Formula (I) and Formula (II)
In the above, R ₅ , R ₆ , and R ₆₆ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. In the general formula (II), Z represents an atomic group consisting of a carbon atom or an oxygen atom capable of forming a 5- or 6-membered condensed heterocycle together with a nitrogen atom and a benzene ring, and m represents 0 to 4 Represents an integer. 2) A silver halide photographic material containing at least one hydrazine derivative represented by the general formula (1) described in 1) is represented by the general formula (I) or the general formula (II) described in 1). An image forming method comprising: treating with a developing solution containing at least one kind of the aminophenol derivative to be used and at least one kind of the compound represented by the general formula (A).

[0016]

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In the general formula (A), R ₇ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. 3) The image forming method according to 2), wherein the image is developed with the developing solution according to 2), wherein the image is substantially free of a dihydroxybenzene-based developing agent. 4) The image forming method according to 3), wherein the silver halide photographic material containing the solid dispersion of the hydrazine derivative according to 1) is subjected to development processing with the developer according to 3). 5) The image forming method according to 3), wherein the developer contains two aminophenol derivatives. However, at least one of the two aminophenol derivatives is
An aminophenol derivative represented by the general formula (I) or the general formula (II) described in 1).

Next, the aminophenol derivative represented by the general formula (I) or (II) used in the present invention will be described in detail.

In the general formulas (I) and (II), R ₁ , R ₂ , R ₃ , R ₄ , R ₁₁ , R ₂₂ , R ₃₃ and R ₇₇ may be the same or different. , Each represents a hydrogen atom or a substituent. Formula (I) and Formula (II)
In the above, R ₅ , R ₆ , and R ₆₆ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. In the general formula (II), Z represents an atomic group consisting of a carbon atom or an oxygen atom capable of forming a 5- or 6-membered condensed heterocycle together with a nitrogen atom and a benzene ring, and m represents 0 to 4 Represents an integer.

In the general formulas (I) and (II), when R ₁ , R ₂ , R ₃ , R ₄ , R ₁₁ , R ₂₂ , R ₃₃ and R ₇₇ represent a substituent, the substituent Examples thereof include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (including an aralkyl group and a cycloalkyl group), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and a quaternized group. Heterocyclic group containing a nitrogen atom (e.g., pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl Group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (ethyl Oxy group or propylene oxy group), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl , Aryl or heterocycle) amino group, nitrogen-containing heterocyclic group (N-substituted), acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoyl Amino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, merca Put group,
(Alkyl, aryl or heterocycle) thio, (alkyl or aryl) sulfonyl, (alkyl or aryl) sulfinyl, sulfo or salts thereof,
Examples include a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a group having a phosphoric acid amide or a phosphoric ester structure, and the like.

These substituents may be further substituted with these substituents. Formula (I) and Formula (II)
In the above, R ₁ , R ₂ , R ₃ , R ₄ , R ₁₁ , R ₂₂ ,
When R ₃₃ and R ₇₇ represent a substituent, the substituent is preferably a halogen atom (for example, a fluorine atom or a chloro atom) or an alkyl group (a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms). For example, methyl, ethyl, isopropyl, cyclopropyl, 2-hydroxyethyl, hydroxymethyl, carboxymethyl, carboxyethyl, aminomethyl, etc.), an acyl group (eg, acetyl, methoxycarbonylacetyl), an alkoxycarbonyl group (eg, methoxycarbonyl), A carbamoyl group (eg, unsubstituted carbamoyl, N-methylcarbamoyl),
A carboxy group or a salt thereof, a carbazoyl group (for example, unsubstituted carbamoyl), an oxamoyl group (for example, unsubstituted oxamoyl), a cyano group, a hydroxy group, an alkoxy group (alkoxy group having 1 to 7 carbon atoms, for example, methoxy, ethoxy, Isopropoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2,3-dihydroxypropoxy, 2- (2-hydroxyethoxy) ethoxy,
-Methanesulfonylethoxy, etc.), an amino group (eg, methylamino, dimethylamino, 2-hydroxyethylamino, carboxymethylamino), an acylamino group (eg, acetamido, propionamido), a sulfonamido group (sulfonamido having 1 to 7 carbon atoms) Groups such as methanesulfonamide, ethanesulfonamide), ureido groups (eg, unsubstituted ureido, N-methylureide), thioureido groups (eg, unsubstituted thioureido,
N-methylthioureido), (alkoxy or aryloxy) carbonylamino group (eg, methoxycarbonylamino), sulfamoylamino group (eg, unsubstituted sulfamoylamino, N′-methylsulfamoylamino), semicarbazide group ( For example, unsubstituted semicarbazide), alkylthio group (alkylthio group having 1 to 7 carbon atoms, for example, methylthio, 2-hydroxyethylthio, 3-hydroxyethylthio, 2- (2-hydroxyethoxy) ethylthio group), alkylsulfonyl group (E.g., methanesulfonyl), a sulfo group or a salt thereof,
Sulfamoyl groups (eg unsubstituted sulfamoyl, N
-Methylsulfamoyl) and the like.

In the general formula (I), R ₅ , R ₆ , R
₆₆ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Here, the alkyl group is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 16 carbon atoms, such as methyl, ethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-hydroxyethyl, 2- (2-hydroxyethoxy) ethyl, 2,3-dihydroxypropyl, 2-aminoethyl, benzyl, 2-acetylaminoethyl,
-Methoxypropyl, 2-methoxyethyl, 1-carboxyethyl, carboxymethyl, 2-methanesulfonylaminoethyl, trimethylammonioethyl, 2-sulfoethyl, 3-carbamoylpropyl and the like.
An alkenyl group is an alkenyl group having 1 to 16 carbon atoms,
For example, vinyl, allyl, styryl, 1-propenyl and the like can be mentioned. The alkynyl group is an alkynyl group having 1 to 16 carbon atoms, such as ethynyl and 1-propynyl. An aryl group is an aryl group having 1 to 16 carbon atoms,
Phenyl, 4-hydroxyphenyl, 2-carboxyphenyl and the like, and a heterocyclic group is a group having 1 to 16 carbon atoms.
5- or 6-membered saturated or unsaturated heterocyclic group such as 2-pyridyl, 2-furyl, 2-imidazolyl and the like.

In the general formula (II), Z represents an atomic group consisting of a carbon atom or an oxygen atom capable of forming a 5- or 6-membered condensed heterocycle in cooperation with a nitrogen atom and a benzene ring. Examples of the condensed hetero ring formed in this case include indole, indoline, dihydroquinoline, tetrahydroquinoline, benzoxazine and the like.

The aminophenol derivative represented by the general formula (I) or the general formula (II) forms a bis-type structure by bonding two kinds directly or via a linking group on an arbitrary carbon atom. You may.

Next, preferred aminophenol derivatives represented by the general formula (I) or (II) will be described. Preferred aminophenol derivatives represented by the general formula (I) are the following general formulas (III):
Preferred aminophenol derivatives represented by the general formula (II) are represented by the following general formula (IV).

[0026]

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Wherein R ₂₀₀ , R ₂₂₀ and R ₇₇₀ represent a hydrogen atom or a substituent, and R ₁₀₀ represents a substituent;
R ₅₀₀ , R ₆₀₀ and R ₆₆₀ are an alkyl group, an alkenyl group,
Represents an alkynyl group, an aryl group, or a heterocyclic group,
n represents an integer of 0 to 4. The substituent represented by R ₁₀₀ is preferably an alkyl group, an alkoxy group, an alkylthio group, a hydroxy group, a carboxy group or a salt thereof, a sulfo group or a salt thereof, an acyl group, a halogen atom, an amino group, an acylamino group, and a sulfonamide. Group, ureido group,
A thioureido group, a sulfamoylamino group, a carbamoyl group, a sulfamoyl group and a sulfonyl group, more preferably an alkyl group, an alkoxy group, an alkylthio group, an acyl group, a halogen atom, an amino group, an acylamino group, a sulfonamide group, and a ureido group , A sulfamoylamino group, a carbamoyl group, and a sulfamoyl group, and the total carbon number of these groups is preferably 10 or less. R
Particularly preferred as the substituent represented by ₁₀₀ is an unsubstituted alkyl group or a substituted alkyl group substituted with a water-soluble group, an alkoxy group, an alkylthio group, an amino group, an acylamino group, a sulfonamide group, a ureido group, and a sulfamoyl. It is an amino group, and it is particularly preferable that the total carbon number of these groups is 8 or less. Here, the water-soluble group refers to a hydroxy group, an alkoxy group, an amino group, an ammonio group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, a carbamoyl group, a sulfamoyl group, a carboxy group or a salt thereof, and a sulfo group. Or a salt thereof. Most preferably, the substituent represented by R ₁₀₀ is an alkoxy group having 1 to 6 carbon atoms in total.

When R ₂₀₀ and R ₂₂₀ represent a substituent, the preferred range is the same as the preferred range of the substituent represented by R ₁₀₀ , but R ₂₀₀ and R ₂₁₀ are particularly preferably a hydrogen atom. R ₇₇₀ is preferably an alkyl group, an alkoxy group, a hydroxy group, a carboxy group (including a salt thereof), or a carbamoyl group;
To 2, most preferably when n represents 0. R ₅₀₀ , R ₆₀₀ , and R ₆₆₀ preferably have a total carbon number of 1
To 10 substituted or unsubstituted alkyl groups, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms in total;
A substituted alkyl group substituted with a water-soluble group having 1 to 6 carbon atoms, wherein the water-soluble group is a hydroxy group, an alkoxy group, an amino group, an ammonium group, an acylamino group, a sulfonamide group, a ureido group, Famoylamino group,
It represents a carbamoyl group, a sulfamoyl group, a carboxy group or a salt thereof, a sulfo group or a salt thereof, and the like. R ₅₀₀ , R
_{Each of 600} and R ₆₆₀ is particularly preferably a methyl group, an ethyl group, or a substituted alkyl group substituted with a water-soluble group having 1 to 4 carbon atoms in total.

Hereinafter, the aminophenol derivatives represented by the general formula (I) or (II) of the present invention will be exemplified, but the present invention is not limited thereto.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7]

The compound of the present invention can be easily synthesized by a known method. Specifically, Japanese Patent Application 8-709
No. 08, the compound can be easily synthesized.

The compound represented by the general formula (I) or (II) is very unstable when stored as a free amine, and thus is generally produced as a salt of an inorganic acid or an organic acid.
It is preferable that the free amine is stored for the first time when it is added to the treatment solution. Formula (I) or (I
Examples of the inorganic and organic acids that form the salt of the compound (I) include hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-1,5-disulfonic acid. Among them, sulfuric acid, naphthalene-
It is preferably a salt of 1,5-disulfonic acid, and most preferably a salt with naphthalene-1,5-disulfonic acid.

The p-aminophenols represented by formula (I) or (II) used as an auxiliary developing agent in the present invention may be used alone or in combination with other known p-aminophenols or 3-pyrazolidones. They can be used in combination. Representative examples of the compounds to be combined are shown below, but are not limited thereto. AP-1 N-methyl-p-aminophenol AP-2 p-aminophenol AP-3 N- (β-hydroxyethyl) -p-aminophenol AP-4 N- (4-hydroxyphenyl) glycine AP-5 2 -Methyl-p-aminophenol AP-6 p-benzylaminophenol AP-7 2-methoxy-p-aminophenol P-1 1-phenyl-3-pyrazolidone P-2 1-phenyl-4,4-dimethyl-3 -Pyrazolidone P-3 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone P-4 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone P-5 1-phenyl-5-methyl-3 -Pyrazolidone P-6 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone P-7 1-p-tolyl- , 4-dimethyl-3-pyrazolidone P-8 1-p- tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone

The compound to be combined is preferably AP-1, AP-3 or AP-7 among the above-mentioned p-aminophenols, and particularly preferably P-2, P-3 or P-8 among the 3-pyrazolidones. It is. Also,
These p-aminophenols are generally used as salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates, and naphthalene-1,5-disulfonates. These compounds can be used in combination of two or more depending on the purpose. In the present invention, the treatment composition may be in a liquid state or a solid state (for example, a powdery state or a granular state).

Next, the case where two kinds of aminophenol derivatives are used in combination will be described in more detail.

In the present invention, it is preferable that the developer containing the ascorbic acid derivative represented by the general formula (A) contains two kinds of aminophenol derivatives. However, at least one of them has the general formula (I) or the general formula (I
The aminophenol derivative of the present invention represented by I).

In addition to the aminophenol derivative of the present invention represented by the general formula (I) or (II), the aminophenol derivatives to be combined here include the following. In the formula (I), compounds wherein R ₆ is a hydrogen atom. (Other than that, the definition of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ is the same as that of the general formula (I) except for metol.) In the general formula (I), R ₅ and R ₅ A compound wherein R ₆ is both hydrogen atoms. (Other than that, R ₁ , R ₂ , R ₃ ,
R ₄ is the same compound as defined in the general formula (I). Where R ₁ , R
_At least one of ₂ , R ₃ and R ₄ represents a substituent. ) Methol (N-methyl-p-aminophenol) A compound in which R ₆₆ is a hydrogen atom in formula (II). (Other definitions are the same as in the general formula (II).)

The preferred combinations of the two aminophenol derivatives include the aminophenol derivatives of the present invention represented by the general formula (I) or (II) (hereinafter simply referred to as the aminophenol derivatives of the present invention). The aminophenol derivative of the present invention and the above compound, a combination of the aminophenol derivative of the present invention and the above compound, or a combination of the aminophenol derivative of the present invention and the above compound, particularly preferably the aminophenol derivatives of the present invention, A combination of the aminophenol derivative of the present invention and the above compound, or the combination of the aminophenol derivative of the present invention and the above compound.

Unexpectedly, when two aminophenol derivatives are used in combination, a high ultimate concentration is observed as a synergistic effect, and the fogging is low in sensitometry and / or the Super hard gradation characteristics were obtained without setting.

In the present invention, the amount of the auxiliary developing agent containing the compound represented by formula (I) or (II) is usually 0.0005 to 0.2 mol / l, preferably 0.1 to 0.2 mol / l.
001 to 0.1 mol / liter, particularly preferably 0.0
It is 1 to 1 mol / liter.

In the present invention, dihydroxybenzenes or ascorbic acids or derivatives thereof are used as a developing agent. Hereinafter, the developing agent will be described in detail.

The dihydroxybenzenes used as a developing agent in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone,
There are 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, hydroquinone monosulfonate and the like, but hydroquinone and hydroquinone monosulfonate are particularly preferable.

As the ascorbic acid or a derivative thereof used as a developing agent in the present invention, a compound represented by the following general formula (A) is preferably used.

[0050]

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In the formula, R ₇ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The ascorbic acid represented by the general formula (A) or a derivative thereof will be described in detail. Where R ₇
The alkyl group represented by is a linear, branched or cyclic alkyl group, an aryl group is, for example, a phenyl group, a naphthyl group or the like, and a heterocyclic group is a carbon atom, a nitrogen atom,
A 5- to 6-membered heterocyclic group composed of an oxygen atom or a sulfur atom, for example, a furyl group, a benzofuryl group,
Pyranyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, pyridyl group, pyrimidyl group, pyridazyl group, thienyl group, isothiazolyl group and the like.
These groups may have a substituent, such as an alkyl group, an alkenyl group, an aryl group, a halogen atom, a nitro group, a mercapto group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, Arylthio group, acyloxy group, amino group, alkylamino group, carbonamide group, sulfonamide group, ureido group, acyl group, oxycarbonyl group, carbamoyl group,
Examples include a sulfinyloxy group, a carboxy group (including a salt), a sulfo group (including a salt), a hydroxyamino group, and a hydrazino group.

Examples of the substituent will be described in more detail. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and even if these groups are substituted with the groups listed as the substituents for R _7. For example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, cyclohexyl, hydroxymethyl and the like can be mentioned. The alkenyl group is a linear or branched alkenyl group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and these groups may be substituted with the groups described as the substituent of R ₇ . For example, ethynyl, propenyl, 3-butenyl, 4-hydroxy-
3-butenyl and the like can be mentioned. The aryl group is an aryl group having 6 to 10 carbon atoms.
It may be substituted by the groups mentioned as the substituent of ₇ , for example, phenyl, naphthyl, p-methylphenyl and the like. The alkoxy group is an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and these groups may be substituted with the groups mentioned as the substituent of R ₇ , for example, methoxy, ethoxy, propoxy. , Butoxy, pentyloxy, hexyloxy, octyloxy, 2-methoxyethoxy, and the like. The aryloxy group is an aryloxy group having 6 to 10 carbon atoms,
These groups may be substituted with the groups mentioned as substituents for R ₇ , for example, phenoxy, p-hydroxyphenoxy, 3,4-dihydroxyphenoxy, o-carboxyphenoxy, o-sulfophenoxy and the like. Can be. The alkylthio group has 1 to 10 carbon atoms,
It is preferably an alkylthio group having 1 to 8 carbon atoms, and these groups may be substituted with the groups mentioned as the substituent of R ₇ , such as methylthio and octylthio. The arylthio group is an arylthio group having 6 to 10 carbon atoms, and these groups may be substituted with the groups described as the substituent of R ₇ , for example, phenylthio, 4-hydroxyphenylthio, 4-methoxyphenylthio , 4-butoxyphenylthio and the like. The acyloxy group has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
8, these groups may be substituted with the groups mentioned as substituents for R ₇ , for example, acetoxy, propanoyloxy, butanoyloxy, octanoyloxy, carboxyacetoxy, 3-sulfopropa Noyloxy and the like can be mentioned.

The alkylamino group is an alkylamino group having 1 to 6 carbon atoms, such as methylamino, dimethylamino and diethylamino. The carbonamido group is a carbonamido group having 1 to 6 carbon atoms, such as an acetamido group and a propionamido group. The sulfonamide group is a sulfonamide group having 1 to 6 carbon atoms, such as a methanesulfonamide group. The ureido group is a ureido group having 1 to 6 carbon atoms, for example, ureido and methylureide. The acyl group is an acyl group having 1 to 6 carbon atoms, such as acetyl and benzoyl. The oxycarbonyl group is an oxycarbonyl group having 1 to 8 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl. The carbamoyl group is a carbamoyl group having 1 to 6 carbon atoms, such as carbamoyl and N, N-dimethylcarbamoyl. The sulfinyloxy group is a sulfinyloxy group having 1 to 6 carbon atoms, such as a methanesulfinyloxy group. These substituents may be further substituted, if possible.

The alkyl group represented by R _{7 in the} general formula (A) is preferably an alkyl group having 1 to 6 carbon atoms,
R ₇ includes those substituted by the groups mentioned as substituents, more preferably, a hydroxy group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
An acyloxy group, an amino group, an alkylamino group, an oxycarbonyl group, a carboxy group (including a salt), an alkyl group substituted with a sulfo group (including a salt), for example,
Methyl, ethyl, hydroxymethyl, 1-hydroxyethyl, 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 1,2,3-trihydroxypropyl,
1,2,3,4-tetrahydroxybutyl, 1,2-dimethoxyethyl, 1,1-dimethoxy-2-hydroxyethyl, 1,2-diethoxyethyl, 1,2-diacetoxyethyl, hydroxycarboxymethyl, Acetoxycarboxymethyl, 1-methylthio-2-hydroxyethyl, 1-phenylthio-2-hydroxymethyl, 1-
Hydroxy-2-octylthioethyl, 1-hydroxy-2-phenylthioethyl, 1-hydroxy-2-aminoethyl, 1-hydroxy-2-phenoxyethyl, 1-
Hydroxy-2-sulfoethyl and the like can be mentioned. These substituents may be further substituted, if possible.

The aryl group represented by R _{7 in the} general formula (A) preferably includes an aryl group having 6 to 10 carbon atoms and substituted by the group mentioned as the substituent of R _7. For example, phenyl, p-methylphenyl, anisyl, p-carboxyphenyl, p-sulfonylphenyl and the like. The heterocyclic group represented by R _{7 in the} general formula (A) preferably includes a furyl group, a pyridyl group, and a triazolyl group, including those substituted by the groups exemplified as the substituent of R _7. , Furyl, 5-methylfuryl, benzofuryl, pyridyl, 5-chloropyridyl,
3-carboxypyridyl, 5-sulfopyridyl, 1-phenyltriazolyl and the like.

R _{7 in the} general formula (A) is particularly preferably a hydrogen atom, a methyl group or an ethyl group, and these groups include those substituted with other substituents. , A hydroxy group, an alkoxy group and an acyloxy group, and more preferably a hydroxy group and an alkoxy group having 1 to 8 carbon atoms. These substituents may be further substituted, if possible. Examples of the substituent include alkenyl groups, aryl groups, hydroxy groups, alkoxy groups, carboxy groups (including salts), and sulfo groups (including salts). ), A hydroxyamino group, a hydrazino group and the like.

Among the compounds represented by the general formula (A), the compound represented by the following general formula (AA) is most preferable.

[0059]

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In the formula, R ₇₇ represents a group represented by formula (AAA) or (AAAA).

[0061]

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In the formula, n represents an integer of 1 to 4. n is preferably 2 or 3, and is most preferably 2.

[0063]

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In the formula, R ₁₇ and R ₁₈ may be the same or different and each represent a hydrogen atom, an alkyl group, an aryl group or an alkenyl group, and the alkyl groups represented by R ₁₇ and R ₁₈ are linked to each other. A ring structure may be formed. Where the alkyl group,
The aryl group and the alkenyl group include those substituted with another substituent, and the substituent includes an alkyl group,
Alkenyl group, aryl group, halogen atom, nitro group,
Examples include a hydroxy group, an alkoxy group, an acyl group, a carboxy group (including a salt), a sulfo group (including a salt), and a hydroxyamino group.

R ₁₇ and R ₁₈ in the compound represented by the general formula (AAAA) are preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, 7
And particularly preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms and an aryl group having 6 to 10 carbon atoms, and most preferably a hydrogen atom or 1 to 7 carbon atoms.
And the alkyl groups represented by R ₁₇ and R ₁₈ may be linked to form a ring structure, and it is more preferable that at least one of them is not a hydrogen atom. These groups may have a substituent, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a chloromethyl group, a methoxymethyl group, a 2-methoxyethyl group, Examples thereof include a 1-hydroxy-2-hydroxyamino-ethyl group and a 2-carboxyethyl group. R ₁₇ ,
Examples of the ring formed by linking the alkyl groups represented by R ₁₈ include a cyclopentyl ring and a cyclohexyl ring, and these groups may be further substituted if possible. Although the compound of the general formula (A) is described as a so-called enol form, the keto form isomerized from this is also the same compound, and in the present application, a compound in which a hydrogen atom is isomerized is also claimed.

Examples of the specific compounds of the present invention include, but are not limited to, the following compounds.

[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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The compound represented by the general formula (A) is ESH
EL.Ashry, A. Moussad, and N. Rashed, Advances in Het
erocyclic Chemistry, vol. 53, 233-302, JP-A-57-1
88586, JP-A-64-45383, JP-A-2-288872, JP-A-4-29985, JP-A-4-364182, JP-A-5-11
The compound can be synthesized according to a general synthesis method such as that described in JP-A No. 2594.

The ascorbic acid represented by the general formula (A) or a derivative thereof used as a developing agent in the present invention may be a free form, an ammonium salt, or an alkali metal salt. The dihydroxybenzenes or ascorbic acids or derivatives thereof used as a developing agent in the present invention may be a free form, an ammonium salt, or an alkali metal salt, and the amount of the dihydroxybenzene or ascorbic acid added to the developing solution is usually 0.01 to
0.5 mol / l, preferably 0.05-0.3 mol / l, particularly preferably 0.05-0.2 mol / l
Liters.

When a combination of a developing agent and an auxiliary developing agent is used, the former is used in an amount of 0.05 to 0.5 mol / l and the latter is used in an amount of 0.01 to 0.1 mol / l. Most preferred.

In the present invention, it is preferable to use a developer (auxiliary developing agent) represented by the general formula (I) or (II) in combination with an ascorbic acid-based developing agent represented by the general formula (A). In this case, it is more preferable that dihydroxybenzenes are not substantially contained. Here, "contains substantially no dihydroxybenzenes" means that the concentration of the dihydroxybenzenes in the developer is represented by the developing agent represented by the general formula (A) or the general formula (I) or (II). Insignificant compared to the amount of auxiliary developing agent (for example, 5 × 1
^0-4 mol / liter or less).

Next, the hydrazine derivative of the present invention represented by the general formula (1) will be described in detail. General formula (1) A- (B) _{m In the} formula, A represents a linking group, B represents a group represented by the following general formula (2), and m represents an integer of 2 to 6. The groups represented by a plurality of Bs linked to A may be the same or different.

[0078]

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In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁₀ represents a hydrogen atom or a block group, and G ₁ represents -CO-, -COCO-, -C = S-,-
SO ₂ —, —SO—, and —PO (R ₃₀ ) — groups (R ₃₀ is R ₁₀
Selected from the same range as the group defined in the above, and may be different from R ₁₀ . ), A thiocarbonyl group, or an iminomethylene group. A ₁₀ and A ₂₀ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (2), the aromatic groups represented by Ar ₁ and Ar ₂ are a monocyclic or condensed-ring arylene group, such as a phenylene group and a naphthylene group. The aromatic heterocyclic group represented by Ar ₁ and Ar ₂ is a monocyclic or condensed-ring aromatic heterocyclic group, for example, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, Groups such as a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Ar ₁ and Ar ₂ are preferably aromatic groups,
More preferably, it is a phenylene group.

Ar ₁ and Ar ₂ may be substituted,
Representative substituents include, for example, halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl Group, heterocyclic group, quaternized nitrogen-containing heterocyclic group (eg, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acyl group Rucarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy group units), aryloxy groups , A heterocyclic oxy group, Siloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocycle) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfone An amide group, a ureido group, a thioureido group, an imide group, an (alkoxy or aryloxy) carbonylamino group,
Sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto Group, (alkyl, aryl or heterocycle) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group Or a salt thereof, a group containing a phosphoric amide or a phosphoric ester structure, and the like.

These substituents may be further substituted with these substituents.

The substituent which Ar ₁ and Ar ₂ may have is preferably an alkyl group having 1 to 20 carbon atoms, an aralkyl group, a heterocyclic group, a substituted amino group, an acylamino group,
Sulfonamide group, ureido group, sulfamoylamino group, imide group, thioureido group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl Groups, carboxyl groups (including their salts), thio groups (including alkyl, aryl, or heterocycles), sulfo groups (including their salts), sulfamoyl groups, halogen atoms, cyano groups, and nitro groups. Ar ₁ is preferably an unsubstituted phenylene group.

In the general formula (2), R ₁₀ represents a hydrogen atom or a block group, and the block group is specifically an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. The alkyl group represented by R ₁₀ is preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoroethyl group,
Examples include a pyridiniomethyl group, a difluoromethoxymethyl group, a difluorocarboxymethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group, and an o-hydroxybenzyl group. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, and examples thereof include a vinyl group, a 2-ethoxycarbonylvinyl group, and a 2-trifluoro-2-methoxycarbonylvinyl group. The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, such as an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed-ring aryl group is preferable, and an aryl group containing a benzene ring is particularly preferable. For example, a phenyl group, 3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 2
-Carbamoylphenyl group, 4-cyanophenyl group, 2
-Hydroxymethylphenyl group and the like. The heterocyclic group is preferably a 5- or 6-membered, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group containing at least one nitrogen, oxygen and sulfur atom, such as a morpholino group, a piperidino group (N -Substitution), imidazolyl group, indazolyl group (such as 4-nitroindazolyl group),
Pyrazolyl, triazolyl, benzimidazolyl, tetrazolyl, pyridyl, pyridinio (N-
Methyl-3-pyridinio group), quinolinio group, quinolyl group and the like. Morpholino, piperidino, pyridyl, pyridinio, indazolyl and the like are particularly preferred. As the alkoxy group, an alkoxy group having 1 to 8 carbon atoms is preferable, and examples thereof include a methoxy group, a 2-hydroxyethoxy group, and a benzyloxy group. As the aryloxy group, a phenoxy group is preferable, and as the amino group, an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized (Including a nitrogen-containing heterocyclic group containing a nitrogen atom). Examples of the amino group include 2,2,6,6-tetramethylpiperidin-4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group and 5
-Benzotriazolylamino group, N-benzyl-3-pyridinioamino group and the like. As the hydrazino group, a substituted or unsubstituted hydrazino group, or a substituted or unsubstituted phenylhydrazino group (such as a 4-benzenesulfonamidophenylhydrazino group) is particularly preferred. The group represented by R ₁₀ may be substituted, and preferred examples of the substituent include those exemplified as the substituents of Ar ₁ and Ar ₂ .

[0085] The R ₁₀ in the general formula (2) disrupts portion of G ₁ -R ₁₀ from the remainder molecule, rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₁₀ moiety of atoms For example, Japanese Unexamined Patent Publication No.
And those described in JP-A-3-29751.

Among the groups represented by R ₁₀ , preferred are
When G ₁ is a —CO— group, a hydrogen atom, an alkyl group,
An alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, or a substituted aryl group (an electron-withdrawing group or an o-hydroxymethyl group is particularly preferred as the substituent); Most preferably, it is an alkyl group. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group, and an amino group are preferred, and a substituted amino group, specifically, an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is particularly preferred. . When G ₁ is a —SO ₂ — group, R ₁₀ is preferably an alkyl group, an aryl group or a substituted amino group.

In the general formula (2), G ₁ is preferably-
It is a CO- group or a -COCO- group, particularly preferably a -CO- group.

In the general formula (2), A ₁₀ and A _{20 each} represent a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a Hammett substituent having a sum of -0.5. A phenylsulfonyl group substituted as described above), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more; Alternatively, a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group (here, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, and a sulfo group. ))). A ₁₀ and A ₂₀ are most preferably a hydrogen atom.

The hydrazine derivative represented by the general formula (1) may have a built-in adsorptive group that adsorbs to silver halide. Examples of such adsorbing groups include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups, which are described in U.S. Pat. Nos. 4,385,108 and 4,459,347; No. 195233, No. 59-200231, No. 59-201045, No. 59-201046, No. 5
Nos. 9-201047, 59-201048, 59
-201049, JP-A-61-170733, and 6
1-270744, 62-948, 63-23
No. 4244, No. 234245, No. 63-234246
And the groups described in (1). These adsorbing groups to silver halide may be precursors. As such a precursor, JP-A-2-285344
And the groups described in (1).

In the general formula (2), the linking groups represented by L ₁ and L ₂ are divalent or trivalent linking groups.
O-, -S-, -N ( _RN )-( _RN represents a hydrogen atom, an alkyl group, an aryl group, or a single bond), -CO
-, - C (= S) -, - SO 2 -, - SO -, - P = O
—, An alkylene group alone, a group composed of a combination of these groups, or a single bond. If Shimese the group consisting of a combination where _{specifically, -CON (R N) -,} -
_{SO 2 N (R N) -} , - COO -, - N (R N) CON
_{(R N) -, - N} (R N) CSN (R N) -, - N (R
_{N) SO 2 N (R N} ) -, - SO 2 N (R N) CO-,
_{-SO 2 N (R N) CON} (R N) -, - N (R N) C
_{OCON (R N) -, -} CON (R N) CO -, - S-
Alkylene group -CONH-, -O-alkylene group -CO
And groups such as NH- and -O-alkylene-NHCO-. In addition, these groups may be connected from either side. When the linking group represented by L ₁ or L ₂ in the general formula (2) contains a trivalent or higher valent group, L ₁ is represented by —Ar ₁ —N (A ₁₀ ) N (A ₂₀₎ -G ₁
A group represented by -R ₁₀ may be linked two or more, and L ₂ is in the general formula _{(2) -Ar 2 -L 1 -Ar} 1
_{-N (A 10) N (A} 20) -G 1 -R 10 group represented by 2
Two or more may be connected. In this case, the trivalent or higher linking group contained in L ₁ and L ₂ is specifically an amino group or a branched alkylene group.

In the general formula (2), L ₁ is preferably -SO ₂ NH-, -NHCONH-, -NHC (= S)
NH-, -OH, -S-, -N (R _N )-, an alkylene group (particularly an active methine group), particularly preferably -SO
₂ NH- group. L ₂ is preferably -CO-, -NH
_{-, - SO 2 -, -} CON (R N) -, - SO 2 N (R
_{N) -, - COO -,} - N (R N) CON (R N) -,
—N (R _N ) CSN (R _N ) — group and the like.

In the general formula (1), the linking group represented by A is a divalent to hexavalent linking group capable of linking the group represented by 2 to 6 represented by B; -S-, -N ( _RN ')-
( _RN ′ represents a hydrogen atom, an alkyl group, an aryl group or a single bond.), —N ⁺ ( _RN ′) ₂ — (the two _RN ′s may be the same or different, and may become a cyclic), - CO -, - C (= S) -, - SO 2
-, -SO-, -P = O-, an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a heterocyclic group alone, or a group formed of a combination of these groups, or a single bond. Here, the arylene group represents a phenylene group or a condensed polycyclic aromatic group, and the heterocyclic group is a saturated or unsaturated heterocyclic group containing a quaternized nitrogen atom such as a pyridinio group. It may be a nitrogen heterocyclic group, specifically, 1,4-
Dioxane ring, piperazine ring, 2,4,8,10-tetraoxaspiro (5,5) undecane ring, biphthalimide ring, 1,2,4,5-benzenetetracarboxydiimide ring, triazine ring, pyridine ring, etc. Is mentioned.
Examples of the cycloalkylene group include those containing a cyclopropane ring, a cyclohexane ring, a bicyclohexane ring, a decalin ring, a norbornene ring, and the like.

In the general formula (1), the linking group represented by A may be substituted, and the substituent is represented by the general formula (2)
And the same substituents as the substituents that Ar ₁ and Ar ₂ may have.

When n is 0 in the general formula (2), the linking group represented by A is a divalent to tetravalent alkylene group, a divalent to hexavalent arylene group, or a divalent to hexavalent group. And at least one of a divalent to hexavalent nitrogen-containing heterocyclic group containing a quaternized nitrogen atom such as a pyridinio group, and a benzene ring. , A naphthalene ring or a heterocyclic group is particularly preferred. Specific examples include the following groups or linking groups containing the partial structures thereof. That is, benzene ring, naphthalene ring, biphenyl, diphenylmethane, diphenyl ether, 1,4-diphenoxybenzene ring, diphenyl sulfide, diphenyl sulfone, triphenylene ring, benzophenone, anthraquinone, imidazole ring, triazine ring, piperazine ring, pyridinio group, dipyridyl ( Bipyridinium group) and the like, and particularly preferably, a benzene ring, a naphthalene ring, biphenyl, diphenyl ether, diphenyl sulfide, and the like.
Diphenyl sulfone, containing a triazine ring,
Most preferably, they include a benzene ring, a naphthalene ring, biphenyl, and diphenyl ether.

In the general formula (2), when n is 1, the linking group represented by A includes —O—, —S—, and —N ( _RN ′).
-( _RN 'represents a hydrogen atom, an alkyl group, an aryl group or a single bond), -N ⁺ ( _RN ') _2- (two _RN '
May be the same or different and may be combined to form a ring), -CO-, -C (= S)-, -SO
_2- , -P = O-, an alkylene group, a cycloalkylene group, an arylene group, a heterocyclic group alone, or a combination of these groups, or a single bond is preferable. Further, -O-, -S-, -N (R _N ')-, -N ⁺ (R _N ')
_{2 -, - CO -, -} C (= S) -, - SO 2 -, an alkylene group, a cycloalkylene group, a single heterocyclic group or a combination of these groups, or a single bond is particularly preferred.

In the general formula (1), m represents an integer of 2 to 6, preferably 2, 3 or 4, particularly preferably 2 or 3.

Specific examples of the hydrazine derivative represented by the general formula (1) are shown below. However, the present invention is not limited to the following compounds.

[0098]

[Table 8]

[0099]

[Table 9]

[0100]

[Table 10]

[0101]

[Table 11]

[0102]

[Table 12]

[0103]

[Table 13]

[0104]

[Table 14]

[0105]

[Table 15]

[0106]

[Table 16]

[0107]

[Table 17]

[0108]

[Table 18]

As the compound represented by the general formula (1),
In addition to those listed here, for example,
No., JP-A-5-197091, WO95-32452
No., WO95-32453, Japanese Patent Application No. 7-351132
No., Japanese Patent Application No. 7-351269, Japanese Patent Application No. 7-35116
8, Japanese Patent Application No. 7-351287, Japanese Patent Application No. 7-3512
Compounds described in No. 79 and the like are mentioned as examples. The compounds of the present invention can be easily synthesized by the methods described in these patents.

The hydrazine compound of the present invention can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, and methylcellosolve. It can be used by dissolving it in, for example. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. A product can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine compound of the present invention may be added to any of the silver halide emulsion layer or another hydrophilic colloid layer on the silver halide emulsion layer side with respect to the support. It is preferably added to the emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the hydrazine compound of the present invention is 1 × with respect to 1 mol of silver halide.
10 ^-6 to 1 × 10 ^-2 mol is preferred, and 1 × 10 ^{-5 to} 5 ×
10 ^-3 mol is more preferred, and 5 × 10 ^{-5 to} 5 × 10 ^-3 mol is most preferred. As the hydrazine compound used in the present invention, in addition to the above, RESEARCHDISCLOSURE I
tem 23516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat.
Nos. 0,207, 4,269,929, 4,27
6,364, 4,278,748, 4,38
5,108, 4,459,347, 4,47
Nos. 8,928, 4,560,638, 4,68
6,167, 4,912,016 and 4,98
8,604, 4,994,365 and 5,04
1,355, 5,104,769, British Patent 2,011,391B, European Patent 217,310
Nos. 301,799, 356,898, JP-A-60-179834, JP-A-61-170733, and 6
1-270744, 62-178246, 62
-270948, 63-29751, 63-3
No. 2538, No. 63-104047, No. 63-121
No. 838, No. 63-129337, No. 63-2237
No. 44, No. 63-234244, No. 63-23424
No. 5, 63-234246, 63-294552
No. 63-306438, No. 64-10233,
JP-A-1-90439, JP-A-1-100530, JP-A-1
No. -105941, No. 1-105943, No. 1-27
Nos. 6128, 1-280747, 1-228354
8, No. 1-283549, No. 1-285940,
2-2541, 2-77057, 2-139
No. 538, No. 2-196234, No. 2-196235
No. 2-198440, No. 2-198441, No. 2-198442, No. 2-220042, No. 2-2
No. 21953, No. 2-221954, No. 2-2853
No. 42, No. 2-285343, No. 2-289843
Nos. 2-302750, 2-304550, 3-37642, 3-54549, 3-125
No. 134, No. 3-184039, No. 3-240036
No. 3-240037, No. 3-259240, No. 3-280038, No. 3-282536, No. 4-5
No. 1143, No. 4-56842, No. 4-84134
No. 2-230233, No. 4-96053, No. 4
-216544, 5-45761, 5-457
Nos. 62, 5-45763, 5-45764, 5-45765, and Japanese Patent Application No. 5-94925 can be used in combination.

In the silver halide photographic light-sensitive material of the present invention, a known nucleation accelerator may be used in combination with at least one of the emulsion layer and the other hydrophilic colloid layer.

The nucleation accelerator used in the present invention includes
Examples include an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. Examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds A-1) to A-73) described in pages 49 to 58. JP-A-7-84
No. 331, (Chem. 21), (Chem. 22) and (Chem. 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12. General formula (1) described in Japanese Patent Application No. 7-37817,
Compounds represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7). 1-1 to 1-19 described
2-1 to 2-22, 3-1 to 3-3
6, compound 4-1 to 4-5, 5-1 to 5-4
1 compound, 6-1 to 6-58 compound and 7-1 to
Compounds 7-38.

The nucleation accelerator preferably used in the present invention is a compound represented by the following formulas (IV), (V), (VI) and (VII).

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In the formula, R ₁₀ , R ₂₀ and R ₃₀ represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocyclic group, and Q represents a nitrogen atom or a phosphorus atom. Represents an atom. L is Q ⁺
And an m-valent organic group bonded by a carbon atom thereof, wherein m represents an integer of 1 to 4. X ^n- represents an n-valent counter anion, wherein n represents an integer of 1 to 3. Where R ₁₀ and R
₂₀ , R ₃₀ or L has an anionic group as a substituent thereof,
When forming an inner salt with Q ⁺ , X ^n- is not required.

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[0118]

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In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent an organic residue containing a quaternized nitrogen atom for completing a substituted or unsubstituted unsaturated heterocycle. B, and C is an alkylene, arylene, alkenylene, _{alkynylene, -SO 2 -, - SO -} , - O -, - S -, - N
( _RN )-, -C = O-, and -P = O- represent a divalent linking group composed of a single compound or a combination thereof. Where R _N
Represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ₁ and R ₂ each represent an alkyl group or an aralkyl group. X ^n- represents an n-valent counter anion, wherein n represents an integer of 1 to 3. However, when an inner salt can be formed, X ^n-
Is not required.

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In the formula, Z contains a quaternized nitrogen atom;
Represents an organic residue for completing a substituted or unsubstituted unsaturated heterocycle. R ₃ represents an alkyl group or an aralkyl group. X ^n- represents an n-valent counter anion, wherein n represents an integer of 1 to 3. However, when an inner salt can be formed, X
^n- is not required.

The general formula (IV) used in the present invention,
The onium salt compounds represented by (V), (VI) and (VII) will be described in detail below.

First, the general formula (IV) will be described in detail. Examples of the groups represented by R ₁₀ , R ₂₀ and R ₃₀ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an octyl group, Straight-chain or branched alkyl groups such as ethylhexyl group, dodecyl group, hexadecyl group and octadecyl group; aralkyl groups such as substituted or unsubstituted benzyl groups; cycloalkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group An aryl group such as a phenyl group, a naphthyl group and a phenanthryl group; an alkenyl group such as an allyl group, a vinyl group and a 5-hexenyl group;
Cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group; alkynyl groups such as phenylethynyl group;
Pyridyl group, quinolyl group, furyl group, imidazolyl group,
Examples include a heterocyclic group such as a thiazolyl group, a thiadiazolyl group, a benzotriazolyl group, a benzothiazolyl group, a morpholyl group, a pyrimidyl group, and a pyrrolidyl group. Examples of the substituent substituted on these groups include R ₁₀ , R ₂₀ ,
The other groups represented by R _30, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom, a nitro group, (alkyl or aryl) amino group, an alkoxy group, an aryloxy group, (alkyl or aryl) Thio group, carbonamido group, carbamoyl group, sulfonamido group,
Examples include a sulfamoyl group, a hydroxyl group, a sulfoxy group, a sulfonyl group, a carboxyl group (including carboxylate), a sulfonic acid group (including sulfonate), a cyano group, an oxycarbonyl group, and an acyl group. L
Examples of the group represented by: when m represents 1, R ₁₀ , R
_20, of the group of R ₃₀ as defined can be mentioned, when the addition to m represents an integer of 2 or more, trimethylene group, tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group, a dodecamethylene group Arylene groups such as polymethylene group, phenylene group, biphenylene group and naphthylene group; polyvalent alkylene groups such as trimethylenemethyl group and tetramethylenemethyl group; phenylene-1,3,5-
And polyvalent arylene groups such as a toluyl group and a phenylene-1,2,4,5-tetrayl group. Examples of the counter anion represented by X ^n- include halogen ions such as chloride ion, bromine ion and iodine ion, carboxylate ions such as acetate ion, oxalate ion, fumarate ion and benzoate ion, and p-toluenesulfonate. , Sulfonate ions such as methanesulfonate, butanesulfonate, and benzenesulfonate, sulfate ions, perchlorate ions, carbonate ions, and nitrate ions.

In the general formula (IV), R ₁₀ , R ₂₀ , R ₃₀
Is preferably a group having 20 or less carbon atoms, and when Q represents a phosphorus atom, an aryl group having 15 or less carbon atoms is particularly preferable. When Q represents a nitrogen atom, an alkyl group having 15 or less carbon atoms, an aralkyl group, Aryl groups are particularly preferred. m is 1
Or 2 is preferred, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group, an aralkyl group, or an aryl group having a total carbon number of 15 or less. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group, an aralkylene group, and these groups and a —CO— group, a —O— group, a —N
(R _N ') -group (R _N ' is a hydrogen atom or R ₁₀ , R ₂₀ , R
Represents a group having the same meaning as ₃₀ and, when a plurality of _RN ′ are present in the molecule, these may be the same or different, and may be bonded to each other), a —S— group, -SO-
And a divalent group formed by combining a group and a —SO ₂ — group. When m represents 2, L is preferably a divalent group having a total carbon number of 20 or less bonded to Q ⁺ at its carbon atom. When m represents an integer of 2 or more, R ₁₀ , R ₂₀ ,
R ₃₀ is present in plural, but a plurality of R _10,
R ₂₀ and R ₃₀ may be the same or different. The counter anion represented by X ^n- is preferably a halogen ion, a carboxylate ion, a sulfonate ion, or a sulfate ion, and n is preferably 1 or 2.

Many of the compounds represented by formula (IV) of the present invention are known and are commercially available as reagents. As a general synthesis method, when Q is a phosphorus atom, a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester; or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. is there. When Q is a nitrogen atom, there is a method in which a primary, secondary or tertiary amino compound is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester. Specific examples of the compound represented by the general formula (IV) are shown below. However,
The present invention is not limited to the following compounds.

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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Next, the general formulas (V) and (VI) will be described in more detail. Where A ₁ , A ₂ , A ₃ , A
₄ represents an organic residue for completing a substituted or unsubstituted unsaturated heterocyclic ring containing a quaternized nitrogen atom,
It may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom, and the benzene ring may be condensed. Examples of the unsaturated hetero ring formed by A ₁ , A ₂ , A ₃ and A ₄ include a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a thiazole ring, a thiadiazole ring, a benzotriazole ring, a benzothiazole ring and a pyrimidine. And a pyrazole ring. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring. The divalent group represented by B or C is an alkylene,
Arylene, alkenylene, alkynylene, -SO ₂ ,
-SO-, -O-, _-S- , -N ( _RN )-, -C = O
-, -P = O- are preferably used alone or in combination. Here, _RN represents an alkyl group, an aralkyl group, an aryl group, or a hydrogen atom. As particularly preferred examples, B and C are alkylene, arylene, -C = O-,-
O-, -S- and -N (R _N )-can be used alone or in combination. R ₁ and R ₂ are preferably an alkyl group having 1 to 20 carbon atoms, and may be the same or different. The alkyl group may be substituted with a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), An unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), (alkyl or aryl) Oxycarbonyl group, sulfo group (including sulfonate), carboxy group (including carboxylate), mercapto group, hydroxy group, alkoxy group (for example, methoxy group, ethoxy group, etc.), aryloxy group, carbonamide group, sulfonamide Group, sulfamoyl group, carbamoyl group, ureido group, thiourei Group, (alkyl or aryl) amino group, a cyano group, a nitro group,
Examples thereof include an alkylthio group and an arylthio group. Particularly preferably, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms. Preferred examples of the substituent include a carbamoyl group, an oxycarbonyl group, an acyl group, an aryl group, a sulfo group (including sulfonate), a carboxy group (including carboxylate), and a hydroxy group. The unsaturated heterocyclic ring formed by A ₁ , A ₂ , A ₃ and A ₄ together with the quaternized nitrogen atom may have a substituent. Examples of the substituent in this case include R ₁ , R
_It is selected from the substituents listed as substituents for the alkyl group of ₂ . The substituent is preferably an aryl group having 0 to 10 carbon atoms, an alkyl group, a carbamoyl group, an (alkyl or aryl) amino group, an oxycarbonyl group, an alkoxy group, an aryloxy group, an (alkyl or aryl) thio group, or a hydroxy group. Carbonyl groups, sulfonamide groups, sulfo groups (including sulfonates), carboxy groups (including carboxylate) and the like. X
^The counter anion represented by ^n- is the same as the general formula (IV), and the preferred range is also the same.

The compounds of the present invention can be easily synthesized by generally well-known methods, but reference is made to the following documents. (See Quart. Rev., 16, 163 (1962).)

Specific compounds of the general formulas (V) and (VI) are shown below, but the present invention is not limited thereto.

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[0136]

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[0137]

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[0138]

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Next, the general formula (VII) will be described in more detail. The nitrogen-containing unsaturated heterocyclic ring containing Z may contain a carbon atom, a hydrogen atom, an oxygen atom, and a sulfur atom in addition to a nitrogen atom, and may further have a benzene ring condensed and have a substituent. May be. Examples of the heterocyclic ring formed include A ₁ , A ₂ ,
The same as the examples of the nitrogen-containing unsaturated hetero ring formed by A ₃ and A ₄ can be mentioned. The preferred range is also the same, and a pyridine ring, a quinoline ring and an isoquinoline ring are preferred. Z
When the nitrogen-containing unsaturated heterocyclic ring having a substituent has a substituent, examples of the substituent include A ₁ in the general formulas (V) and (VI),
Examples of the substituent which the nitrogen-containing unsaturated heterocyclic ring formed by A ₂ , A ₃ and A ₄ may have are the same as those mentioned above, and the preferred range is also the same. R ₃ represents an alkyl group or an aralkyl group, which has 1 to 20 carbon atoms, may be substituted or unsubstituted, and may be linear, branched, or cyclic. The substituent is represented by the general formula (V)
Examples of the substituent which the alkyl group represented by R ₁ and R ₂ may have are the same as those described above, and the preferred range is also the same. The counter anion represented by X ^n- is the same as that in formula (IV), and the preferred range is also the same.

The compound represented by the general formula (VII) of the present invention can be easily synthesized by a generally well-known method, but reference is made to the following documents. (See Quart.
Rev., 16, 163 (1962).)

Next, specific examples of the compound represented by the general formula (VII) of the present invention are shown below, but the present invention is not limited thereto.

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[0143]

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As the amino compound preferably used in the present invention as a nucleation accelerator, the following compounds are used.

The compound described in JP-A-7-84331 (Formula 2)
1) Compounds represented by (Chemical Formula 22) and (Chemical Formula 23), specifically, compounds described on pages 6 to 8 of the same publication. Compounds represented by the general formula [Na] described in JP-A-7-104426, specifically, compounds Na-1 to Na-22 described on pages 16 to 20 of the same. Japanese Patent Application No. 7-37817
Compounds represented by general formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (6) and general formula (7) described in Specifically, the compounds of 1-1 to 1-19 described in the same specification, 2-1 to 2-
22 compounds, 3-1 to 3-36 compounds, 4-1 to 4
-5, 5-1 to 5-41, 6-1 to 6
The compound of -58 and the compounds of 7-1 to 7-38.

The nucleation accelerator of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methyl It can be used by dissolving it in Cellsolve or the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The nucleation accelerator of the present invention may be added to any layer of the silver halide emulsion layer or another hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × 10 per mol of silver halide.
^-2 mol is preferable, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferable, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferable.

The silver halide emulsion according to the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide and silver iodobromide as silver halide. It is preferably at least 50 mol%, more preferably at least 50 mol%.
The content of silver iodide is preferably at most 5 mol%, more preferably at most 2 mol%.

The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but is preferably cubic or tabular.

The photographic emulsion used in the present invention is P. Glafki.
by des Chimie et Physique Photographique (Paul Mont
el, 1967), Photographic Emulsi by GFDufin
on Chemistry (The Focal Press, 1966), VLZeli
Making and Coating Photographic Emuls by kman et al
ion (The Focal Press, 1964) and the like.

That is, any of an acidic method and a neutral method may be used, but it is preferable to carry out under acidic conditions. As a method for reacting the soluble silver salt and the soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds, described in JP-A-53-82408 and JP-A-55-7.
No. 7737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent varies depending on the type of the compound used, the target grain size, and the halogen composition.
It is preferably from 0 ^-5 to 10 ^-2 mol.

According to the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method in which the addition rate of silver nitrate or alkali halide is changed in accordance with the grain growth rate, a method disclosed in British Patent No. 4,242,445, JP-A-55-15812
It is preferable to use the method of changing the concentration of the aqueous solution as described in No. 4 to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodispersed emulsion, and {(standard deviation of particle size) / (average particle size)} ×
The coefficient of variation represented by 100 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.08 μm to 0.4 μm.

The silver halide emulsion used in the present invention is
It may contain a metal belonging to Group VIII. In order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, a rhenium compound, a chromium compound and the like. Preferred as these heavy metals are metal coordination complexes, and hexacoordinate complexes represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (where M is a heavy metal selected from Ir, Ru, Rh, Re, and Cr; L is a bridging ligand; and Y is oxygen or sulfur) M = 0, 1, 2 and n = 0, −1, −
2, -3. Preferable examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyanate Nate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. In order to increase the sensitivity, an iron compound is preferably contained, and a metal coordination complex having a cyan ligand as a ligand is particularly preferable. These compounds are used by dissolving them in water or a suitable solvent, and are generally used to stabilize the solution of the compounds, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid, etc.), Alternatively, an alkali halide (for example, KC
1, NaCl, KBr, NaBr, etc.). It is also possible to add and dissolve another silver halide grain doped with these compounds in advance. Specific examples of the metal coordination complex are shown below. 1. [Rh (N ₂ O) Cl _5] ^-2 2. [RuCl ₆ ] ^-3 3. [Ru (NO) Cl _5] ^-2 4. [RhCl ₆ ] ^-3 5. [Ru (H ₂ O) Cl _5] ^-2 6. _{[Ru (NO) (H 2 O} ) Cl 4 ] ^-1 7. [Ru ₂ Cl ₁₀ O] ^-2 8 [Re (NO) Cl ₅ ] ^-2 9. [Ir (NO) Cl ₅ ] ^-2 10. [Ir (H ₂ O) Cl ₅ ] ^-2 11. [Re (H ₂ O) Cl ₅ ] ^-2 12. [RhBr ₆ ] ^-3 13. [ReCl ₆ ] ^-3 14. [IrCl ₆ ] ^-3 15. [Re (NS) Cl ₄ (SeCN)]- ² . [Cr (CN) ₆ ] ^-3 17. [Fe (CN) ₆ ] ^-3

The addition amount of these compounds is 1 × 10 ^-8 to 1 × 10 ^-2 mol, preferably 5 × 10 ^-8 to 2 × 10 ^-4 mol, per mol of silver of the silver halide emulsion. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. .

The silver halide emulsion of the present invention is preferably subjected to chemical sensitization. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Known compounds can be used as the sulfur sensitizer.For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Other US Patent No. 1,57
No. 4,944, No. 2,410,689, No. 2,2
No. 78,947, No. 2,728,668, No. 3,
Nos. 501,313 and 3,656,955, German Patent 1,422,869, JP-B-56-2
No. 4,937, JP-A-55-45016 and the like can also be used. Preferred sulfur compounds are thiosulfates and thiourea compounds. The addition amount of the sulfur sensitizer varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains.
The amount is 10 ^-7 to 10 ^-2 mol, preferably 10 ^{-5 to} 5 × 10 ^-4 mol, per mol of silver halide.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798. Further, a low-decomposition active selenium compound can also be preferably used. The low-decomposition active selenium compound is a mixed solution of 10 mmol of AgNO ₃ , 0.5 mmol of selenium compound, and 40 mmol of 2- (N-morpholino) ethanesulfonic acid buffer in a water / 1,4-dioxane volume ratio of 1/1 ( pH =
6.3) is a selenium compound having a half-life of 6 hours or more when reacted at 40 ° C. This low-decomposition active selenium compound is disclosed in Japanese Patent Application No. 7-28881.
It is preferable to use the compounds of Compound No. 04, SE-1 to SE-10.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102 (19)
79), ibid 645 (1979), Journal of Chemical
Society Parkin Transaction (J.Che
m.Soc.Perkin.Trans.) 1,2191 (1980), S.Pata
i) Ed., The Chemistry of Organic Selenium and Tellurium Campounds
istry of Organic Serenium and Tellunium Compounds),
The compounds described in Vol. 1 (1986) and Vol. 2 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, and the like, but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably 10 ^{−7 to} 5 × 10
^Use about ^-4 moles. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, and the pAg
Is 6-11, preferably 7-10, and the temperature is 40-95 ° C, preferably 45-85 ° C.
As the noble metal sensitizer used in the present invention, gold, platinum,
Palladium, iridium and the like can be mentioned, but gold sensitization is particularly preferable. The gold sensitizer used in the present invention may have an oxidation number of gold of +1 or +3. Specifically, chloroauric acid,
Potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide and the like, and 10 ^-7 to 10 ⁻ per mol of silver halide. ^{About 2} moles can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. The silver halide emulsion of the present invention is disclosed in European Patent (EP) -2.
A thiosulfonate compound may be added by the method described in No. 93,917. The addition amount of the thiosulfonic acid compound varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains, but it is 1 × 10 ⁻⁷ mol or more per mol of silver halide. ,
It is preferably at most 5 × 10 ^-2 mol. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind,
Two or more (for example, those having different average grain sizes, different halogen compositions, different crystal habits, and different chemical sensitization conditions) may be used in combination. The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to a relatively long wavelength blue light, green light, red light or infrared light by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Item 1
These are described in the documents described or cited in Item 7631IV-A (December 1978, p.23) and Item 1831, Item X (August 1979, p.437). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected. For example,
A) For an argon laser light source, see JP-A-60-1
Compounds of (I) -1 to (I) -8 described in No. 62247, and I-1 to I-2 described in JP-A-2-48653.
Compound No. 8 described in I-1 described in JP-A-4-330434
To I-13, U.S. Pat. No. 2,161,331
The compounds of Examples 1 to 14 described in JP-A No. 136,071 and the compounds of Examples 1 to 7 described in German Patent No. 936,071 and B) a helium-neon laser light source are disclosed in
Compounds I-1 to I-38 described in JP 18726, compounds I-1 to I-35 described in JP-A-6-75322, and compounds I-1 to I-34 described in JP-A-7-287338. C) For LED light sources, dyes 1 to 20 described in JP-B-55-39818;
Compounds of I-1 to I-37 described in JP-A-2-284343 and compounds of I-1 to I-34 described in JP-A-7-287338; I-1 to I-1 described in No. 191032
Compound I-2 described in JP-A-60-80841
To I-22, the compounds of I-1 to I-29 described in JP-A-4-335342, and the compound of JP-A-59-1.
Compounds of I-1 to I-18 described in No. 92242,
E) For the tungsten and xenon light sources of the plate making camera, the general formula [I] described in JP-A-55-45015
Compounds (1) to (19) represented by the following formula:
No. 6193, compounds of I-1 to I-97 and JP-A-6-24247, compounds of 4-A to 4-S, compounds of 5-A to 5-Q, and compounds of 6-A to 6- T
Are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosu.
re) Volume 176, 17643 (issued December 1978) No. 2
Section J on page 3, IV, or the aforementioned JP-B-49-25500
No. 43-4933, JP-A-59-19032,
No. 59-192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025 and the like, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-5-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As disclosed in Japanese Patent No. 74624, a method of dissolving a dye using a compound that causes red shift and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the silver halide grain forming step and / or before the desalting, during the desilvering step and / or after the desalting. Previous period, Japanese Patent Application Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after the chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A No. 58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or when the chemical ripening is completed. May be added separately, such as before or after chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added and divided. Good.

The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5. Specifically, compounds (III) -1 to 25 described in the publication.

Compounds represented by the general formula (I) described in JP-A-1-11832 and having substantially no absorption maximum in the visible region. Specifically, compound I-
Compounds 1 to I-26.

Antifoggants described in JP-A-2-103536, page 17, lower right, line 19 to page 18, upper right, fourth line.

The polymer latex described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20. General formula (I) described in Japanese Patent Application No. 8-13592.
A polymer latex having an active methylene group represented by the formula:
6. A polymer latex having a core / shell structure described in Japanese Patent Application No. 8-13592, specifically, compounds P-1 to P-55 described in the same specification.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15;

Hardeners described in JP-A-2-103536, page 18, upper right line, 5th line to upper right line, 17th line.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right, line 6 to page 19, upper left, first line.

JP-A-2-18542, page 2, lower left 1
The conductive substance described in the third line to the upper right line on page 3 of the publication. Specifically, the metal oxides described on page 2, lower right line 2 to page 10, lower right line, and the conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right, line 1 to upper right, line 18;

Solid disperse dyes represented by formula (FA), formula (FA1), formula (FA2) and formula (FA3) described in Japanese Patent Application No. 7-350753. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
(II-2) to (II-24) described in JP-A-7-152
No. 112, (III-5) to (III-18);
Nos. 152112 to (IV-2) to (IV-7).

Solid disperse dyes described in JP-A-2-294638 and JP-A-3-185773.

JP-A-2-12236, page 9, upper right 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds VI-1 to VI-15 described in the publication.

The following nucleation accelerators such as amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. JP-A-7-77783, page 48, line 2 to
Compounds described in line 37, specifically, compounds A-1) to A-73) described on pages 49 to 58. JP-A-7-843
(Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12. General formula (1) described in Japanese Patent Application No. 7-37817,
Compounds represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7). 1-1 to 1-19 described
2-1 to 2-22, 3-1 to 3-3
6, compound 4-1 to 4-5, 5-1 to 5-4
1 compound, 6-1 to 6-58 compound and 7-1 to
Compounds 7-38.

The following hydrazine derivatives are disclosed in Japanese Patent Application No.
No. 47961, a compound represented by the general formula (I), specifically, a compound represented by I-1 to I-53 described in the same specification. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082.
The compound of 1-38 on page 18. JP-A-6-2304
No. 97, compounds represented by the general formula (4), the general formula (5) and the general formula (6).
Compounds 4-1 to 4-10, 2 described on page 26.
Compounds 5-1 to 5-42 described on pages 8 to 36, and compounds 6-1 to 6-7 described on pages 39 and 40.
Compounds represented by general formulas (1) and (2) described in JP-A-6-289520.
Compounds 1-1) to 1-17) and 2 described on pages 7 to 9
-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936.
Compounds described on page 19 to page 19. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (1) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same. Compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H-1 to H-44 described on pages 8 to 15 of the same publication. A compound described in Japanese Patent Application No. 7-191007 characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group, and particularly a compound represented by the general formula (A) ), General formula (B), general formula (C), general formula (D),
Compounds represented by formulas (E) and (F), specifically, compounds N-1 to N-30 described in the publication. Compounds represented by the general formula (1) described in Japanese Patent Application No. 7-191007, specifically, compounds D-1 to D-
55.

A redox compound capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816, preferably a compound represented by the general formula (R-1) described in the same.
Redox compounds represented by the general formulas (R-2) and (R-3). Specifically, compound R-1 described in the publication
~ R-68.

JP-A-2-18542, page 3, lower right 1
The binder described in the second to 20th lines.

The processing agents such as the developing solution and the fixing solution and the processing method in the present invention will be described below. However, it is needless to say that the present invention is not limited to the following description and specific examples.

For the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used.

The developer used for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. Examples of the buffer used in the developer for developing the light-sensitive material in the present invention include carbonates, boric acid described in JP-A-62-186259, and saccharides described in JP-A-60-93333 (for example, saccharose). ), Oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like,
Preferably, carbonate and boric acid are used. The amount of buffer, especially carbonate, used is preferably at least 0.1 mol / l, in particular 0.2 to 1.5 mol / l.

Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is more than 0.2 mol / l, especially 0.3
It is used in an amount of at least mol / l, but if it is added in too large an amount, it causes silver contamination in the developing solution.
Desirably, it is mol / liter. Particularly preferably,
It is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite.
Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Other additives used in addition to the above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (for example, 3- (5
-Mercaptotetrazol-1-yl) benzenesulfonic acid sodium salt, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventive agents. In addition, mercapto-based compounds, indazole-based compounds, benzotriazole-based compounds, and benzimidazole-based compounds are used as antifoggants or black pepper.
It may be included as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4- (2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4- Thiadiazole-2-
Examples thereof include thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Further, various kinds of organic,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. As the organic carboxylic acid, for example,
Acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, itaconic acid, malic acid , Citric acid, tartaric acid and the like.

Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycolethertetraacetic acid, and the like.
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others, JP-A-52-25632 and JP-A-55-67747. And JP-B-57-102624 and JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3,214,454 and 3,794,591 and German Offenlegungsschrift 2,227,369, and Research Disclosure, Vol. 18170 (May 1979) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition, the above-mentioned Research Disclosure 18170, JP-A-57-20855.
No. 4, 54-61125, 55-29883,
Compounds described in JP-A-56-97347 and the like can be mentioned.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726 and 53-42730,
Nos. 54-112127, 55-4024, and 55
No.-4025, No.55-126241, No.55-65
No. 955, No. 55-65556 and the compounds described in Research Disclosure 18170 mentioned above.

The organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol per liter of the developer.

Further, as a silver stain inhibitor in the developer,
For example, JP-A-56-24347, JP-B-56-465.
No. 85, JP-B-62-2849, JP-A-4-3629
No. 42, JP-A-8-6215, and triazines having at least one mercapto group (for example, compounds described in JP-B-6-23830, JP-A-3-282457, and JP-A-7-175178). ) And the same pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine,
5,6-diamino-2,4-dimercaptopyrimidine,
2,4,6-trimercaptopyrimidine and the like pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,
4,6-trimercaptopyridine, JP-A-7-2485
No. 87), the same pyrazine (eg, 2-
Mercaptopyrazine, 2,6-dimercaptopyrazine,
2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc., and the same pyridazines (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine,
3,5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177, polyoxyalkyl phosphonates described in U.S. Pat. No. 5,457,011, and the like. Can be used. These silver stain inhibitors can be used alone or in combination of two or more. The addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol, per liter of the developer. In addition, as a dissolution aid,
The compound described in 1-267759 can be used. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent,
It may contain a hardener and the like.

The preferred pH of the developer is from 9.0 to 12.0.
And particularly preferably in the range of 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As the cation of the developing solution, potassium ions do not suppress the development as compared with sodium ions, and there is less jaggedness around the blackened portion called fringe. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, it is preferable that the molar ratio of potassium ion to sodium ion in the developer is between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishment amount of the developing solution was 3 per m ² of the light-sensitive material.
90 ml or less, preferably 325 to 30 ml, and 180
~ 120 ml is most preferred. The development replenisher may have the same composition and / or concentration as the development start solution, or may have a different composition and / or concentration from the start solution.

As the fixing agent of the fixing processing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent used can be changed as appropriate, but is generally about 0.7 to 0.7.
It is about 3.0 mol / liter.

The fixing solution in the present invention may contain a water-soluble aluminum salt and a water-soluble chromium salt used as a hardener, and a water-soluble aluminum salt is preferable. For example, aluminum chloride, aluminum sulfate, potassium alum,
Examples include aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are preferably contained at a concentration of 0.01 to 0.15 mol / l as an aluminum ion concentration in the working solution. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

If necessary, a preservative (for example, a sulfite, a bisulfite, a metabisulfite, etc.) may be used in the fixing treatment agent.
5 mol / l or more, preferably 0.02 mol / l or more
0.3 mol / l), pH buffer (eg, acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate, phosphoric acid, succinic acid, adipic acid, etc.) at 0.1 mol / l to 1
Mol / l, preferably 0.2 mol / l to 0.7 mol / l), compounds having aluminum stabilizing ability or water softening ability (eg gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, apple Acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tyrone, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and derivatives thereof and these 0.001 mol / L to 0.5 mol / L, preferably 0.005 mol / L to 0.3 mol / L).

In addition, compounds described in JP-A-62-78551, pH adjusters (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators, and the like can be included. As the surfactant, for example, anionic surfactants such as sulfated sulfone oxide,
Examples include polyethylene surfactants and amphoteric surfactants described in JP-A-57-6840, and known antifoaming agents can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B-45-35754, JP-B-58-122535, and JP-A-58-122535.
Thiourea derivative described in 8-122536, 3 in the molecule
Alcohols with heavy bonds, U.S. Pat. No. 4,126,4
No. 59, thioether compounds described in JP-A-64-473;
9, mercapto compounds described in JP-A-1-4739, JP-A-1-159645 and JP-A-3-101728,
It can contain the mesoionic compound and thiocyanate described in JP-A-4-170539.

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 6.0. In the fixer, the pH rises due to the mixing of the developer with the processing, but in this case,
It is 6.0 or less, preferably 5.7 or less for a hardened fixer, and 7.0 or less, preferably 6.7 or less for a non-hardened fixer.

The replenishment rate of the fixing solution is 5 per m ² of the photosensitive material.
00 ml or less, preferably 390 ml or less,
80 ml is more preferred. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

The photosensitive material which has been subjected to the development and fixing processing is then washed or stabilized (hereinafter, unless otherwise specified, the washing including the stabilization processing is performed. The liquid used for these is water or washing water. .) Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be less. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When the washing is performed with a low replenishing amount, see Japanese Unexamined Patent Publication No.
It is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A Nos. 18350 and 62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method for reducing the replenishing amount of washing, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time. The replenishing amount of washing is 200 to 50 ml per 1 m ² of the photosensitive material.
Is preferred. This effect is achieved by the independent multi-stage method (
A method of replenishing a new solution individually in a multi-stage washing tank) can also be obtained in the same manner.

Further, in the method of the present invention, a scale preventing means may be provided in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. Other than the aforementioned oxidizing agents, for example, glutaraldehyde,
There are chelating agents such as aminopolycarboxylic acids, cationic surfactants, and mercaptopyridine oxides (eg, 2-mercaptopyridine-N-oxide), which may be used alone or in combination. As a method of energizing,
The methods described in JP-A-3-224885, JP-A-3-224687, JP-A-4-16280, and JP-A-4-18980 can be used.

In addition, a known water-soluble surfactant or defoaming agent may be added to prevent unevenness of water bubbles and transfer of dirt. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing system to prevent contamination by the dye eluted from the photosensitive material.

As described in JP-A-60-235133, a part or all of the overflow solution from the washing step can be mixed and used with a processing solution having a fixing ability. In addition, microbial treatment (for example, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic, etc.), and oxidation treatment with an electric current or an oxidizing agent are performed to obtain biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use a polymer having affinity for silver, or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering the mixture with a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment. Examples thereof include JP-A-2-201357, JP-A-2-132435, JP-A-1-102553, and JP-A-4-102553.
A bath containing the compound described in JP-A-6-44446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath may also contain a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, a deterrent, an alkanolamine or a surfactant. Agents can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths and the stabilizing agents can be solid agents as in the above-mentioned developing and fixing processing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is incinerated. These waste liquids are described in, for example, Japanese Patent Publication No. 7-83867, U.S. Pat.
It is also possible to condense or solidify with a concentrating device as described in S5439560 or the like before disposing.

To reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent evaporation of the liquid and air oxidation. U.S. Pat. Nos. 3,025,779 and 3,545, for roller-transfer type automatic developing machines.
No. 971 and the like, and are simply referred to as a roller transport type automatic developing machine in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps.
Further, a rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, 25 to 25 dry to dry
To 160 seconds, the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each liquid is 25 to 50 ° C.
Is preferable, and 30 to 40 ° C. is preferable. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation. However, hot air drying, JP-A-4-15534, and JP-A-4-15534 can be used.
Heat roller drying and drying by far-infrared rays as disclosed in JP-A Nos. 256 and 5-289294, and a plurality of methods may be used in combination.

When the developing and fixing processing agent in the present invention is a liquid, it is preferable to store it in a packaging material having low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Although the developing agent and the fixing agent in the present invention can obtain the same result as the liquid agent even when they are solids, the solid processing agents will be described below. The solid agent in the present invention,
Known forms (powder, granule, granule, block, tablet, compactor, briquette, plate, stick, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may decompose components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating auxiliaries can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 48, line 48 to column 3, line 13 can be referred to.

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets, briquettes or the like. It may be packaged in a similar layer configuration. These methods are described in, for example, JP-A-61-259921,
-16841, 4-78848, 5-9399
No. 1 etc.

The solid processing agent has a bulk density of 0.5 to 6.0 g.
/ Cm ³ is preferable, and especially, the tablet is 1.0 to 5.0 g / cm ^3.
The granules are preferably 0.5 to 1.5 g / cm ³ .

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, JP-A-4-78
No. 848, No. 5-93991, JP-A-4-85533.
Nos. 4-85534, 4-85535, 5-
134362, 5-197070, 5-204
Nos. 098, 5-224361, 6-138604
No. 6,138,605, and Japanese Patent Application No. 7-89123.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, Japanese Patent Laid-Open No. 6-242 is disclosed.
Nos. 585 to 6-242588 and 6-247432
No. 6-247448, Japanese Patent Application No. 5-30664,
JP-A-7-5664, JP-A-7-5666 to JP-A-7-56
It is also preferable to adopt a foldable shape as disclosed in No. 69 in order to reduce the storage space of the waste packaging material. For these packaging materials, a screw cap, a pull-top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and the limitation is particularly limited. do not do. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and Japanese Patent Application No. Hei 7 (1994) -197686.
Dissolving in a dissolving apparatus having a dissolving part and a part for storing a finished liquid as described in US Pat.
Replenishment method from stock section, Japanese Patent Laid-Open No. 5-119454
No. 6-19102 and No. 7-261357, a method of introducing and dissolving and replenishing a processing agent into a circulating system of an automatic developing machine, a photosensitive material using an automatic developing machine having a built-in dissolving tank. There is a method of adding and dissolving the treating agent in accordance with the above treatment, but any other known method can be used. The processing agent may be charged or may be obtained, or may be automatically opened and automatically loaded by a dissolution apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferred in terms of working environment. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method described in JP-A-6-191 are disclosed.
02 and 6-95331.

[0222]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto.

Example 1 The following developer was prepared. <Developer composition> Developing agents shown in Table 19 Aminophenol derivatives shown in Table 19 Diethylenetriamine-5-acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium hydrogen carbonate 25 g KBr 2 g 5-Methylbenzotriazole 0.004 g 1-phenyl-5-mercapto Tetrazole 0.02 g Sodium sulfite 2 g Add water to 1 liter and adjust pH to 9.7.

[0224]

[Table 19]

The hydrazine derivatives 1c, 5c
e, a solid dispersion of 25c was prepared. <Adjustment of solid dispersion of hydrazine compound> Demol SNB
A 25% aqueous solution of (Kao Corporation) was prepared. Next, 1.2 g of the above-mentioned Demol SNB aqueous solution and 59 g of water were added to 1 g of the hydrazine derivative and mixed to form a slurry.
This slurry was placed in a dispersing machine (1/16 gallon, sand grinder mill (manufactured by Imex Co., Ltd.)), and 170 g of glass beads having a diameter of 0.8 to 1.2 mm were used as a medium.
For 15 hours. Next, an aqueous gelatin solution was added and mixed so that the hydrazine compound concentration was 1% and the gelatin concentration was 5%, and 2000 ppm of proxel was added to gelatin as a fungicide. Finally, the pH was adjusted to 5.0 by adding ascorbic acid. The average particle size of the obtained solid dispersion was about 0.3 μm.

A light-sensitive material was prepared as follows. <Emulsion preparation> 1 liquid 1 liter of water 20 g of gelatin 20 g of sodium chloride 3.0 g of 1,3-dimethylimidazolidin-2-thione 20 mg of sodium benzenethiosulfonate 8 mg of 2 liquids of water 400 ml of silver nitrate 100 g of 3 liquids of water 400 ml of sodium chloride 27.1 g of odor Potassium iodide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridate (III) (0.001% aqueous solution) 6 ml

Solution 2 and solution 3 were added simultaneously to solution 1 maintained at 42 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

Thereafter, the product was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was performed so that the sensitivity was the highest at ℃. Further, 4-hydroxy-6-methyl-1,3,3a,
100 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally a silver chloroiodobromide cubic emulsion A containing 70 mol% of silver chloride and having an average grain size of 0.25 μm.
I got

<Preparation of Coated Sample> Sensitizing dye (1) was added to the emulsion.
3.8 × 10 ^-4 mol / mol Ag was added for spectral sensitization. Further, KBr (3.4 × 10 ⁻⁴ mol / mol Ag), compound (1) 3.2 × 10 ⁻⁴ mol / mol Ag, compound (2) 8.
0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 1
0 ^-2 mol / mol Ag, citric acid 3.0 × 10 ^-3 mol / mol Ag, and the hydrazine derivatives shown in Table 20 were added in an amount of 1.0 × 10 ³ mol / mol Ag.
^-4 mol / mol Ag, compound (4) was 6.0 × 10 ^-4 mol / mol.
Mole Ag, 35 wt% polyethyl acrylate latex based on gelatin, 20 wt% based on gelatin
Colloidal silica having a particle size 10mμ of, 4 wt% of the compound with respect to the gelatin (5) was added, Ag2.5g / m ² on a polyester support was coated to a gelatin 1.2 g / m ^2. On this, a protective layer upper layer and a protective layer lower layer of the following composition, and a UL layer of the following composition under this were applied.

Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (6) (Gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (7) 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (8) 20 mg / m ² Underlayer of protective layer Gelatin 0.5 g / m ² Compound (9) 15 mg / m ² 1,5-dihydroxy-2 - benzaldoxime 10 mg / m ² of polyethyl acrylate latex 150 mg / m ²

UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (5) 40 mg / m ² Compound (10) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions.

Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinyl Sulfonyl-2-propanol 60 mg / m ² Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (5) 120 mg / m ²

Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ²

[0235]

Embedded image

[0236]

Embedded image

[0237]

[Table 20]

<Evaluation> (1) Exposure and development treatment The above sample was exposed to xenon flash light having an emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 633 nm, and the above developer was used. Fuji Photo Film's AP-560 automatic processor, 34
After development at 15 ° C. for 15 seconds, fixing, washing and drying were performed.

As the fixing solution, a fixing solution having the following formulation was used. <Fixing solution> Ammonium thiosulfate 120 g Ethylenediamine / tetraacetic acid / 2Na / dihydrate 0.03 g Sodium thiosulfate / pentahydrate 11 g Sodium metasulfite 19 g Sodium hydroxide 12.4 g Acetic acid (100%) 30 g Tartaric acid 2.9 g Gluconic acid Sodium 1.7 g Aluminum sulfate 8.4 g pH 4.8

(2) Evaluation (gamma) As an index (gamma) indicating the contrast of an image, fog + is determined from the point of fog + density of 0.1 on the characteristic curve.
Points having a density of 3.0 were connected by a straight line, and the slope of the straight line was expressed as a gamma value. That is, gamma = (3.0-0.
1) / (log (exposure to give a density of 3.0) -log (exposure to give a density of 0.1)], indicating that the larger the gamma value, the harder the photographic characteristics. When the value is 15 or less, it is not practically usable, and is preferably 20 or more.

(3) Practical Dmax Test steps (16 steps) using a helium-neon light source color scanner SG-608 manufactured by Dainippon Screen Co., Ltd. while changing the LS value (light step value) at 175 lines / inch. And the development processing was performed under the processing conditions described above, and the density of the solid portion when exposed at an LS value at which the halftone dot on the eighth stage was 49% was defined as the actual skill Dmax. Oh, net% is Ma
It was measured using cbeth TD904. Practical skill Dmax is 4.
If it is 0 or less, it is not practical and it is preferably 4.5 or more.

(4) Evaluation of Linear Reproducibility A test step (16 steps) was output at 175 lines / inch using a helium-neon light source color scanner SG-608 manufactured by Dainippon Screen Co., Ltd. The development processing was performed under the conditions, and when the halftone dot on the eighth stage became 49%, the halftone dot ratio on the first and fifteenth stages was measured. The first stage is 5%,
The closer the 15th stage is to 92%, the better the linearity. In addition, the net% was measured using Macbeth TD904. If the first stage is 3% or less and the 15th stage is 94% or more, it is not practical.

(5) Evaluation of Sharpness of Halftones Using an argon light source color scanner M-656 manufactured by Crossfield Co., Ltd., a 50% flat screen was output to the coated light-sensitive material at 100 lines, and the conditions described above were applied. Perform development processing under the conditions,
The sharpness of halftone dots was visually evaluated with a 200-fold loupe. The evaluation results are shown in the table by a five-point method of (good) 5 to 1 (bad). Practically, three or more points are required.

The evaluation results are shown in Table 21.

[0245]

[Table 21]

<Results> When the light-sensitive material containing the hydrazine derivative of the present invention and the developer of the present invention are combined, specifically, all the properties of ultra-high contrast, practical Dmax, linear reproducibility, and halftone dot sharpness are obtained. Was obtained.

Example 2 A running test was performed using FG-520AG manufactured by Fuji Photo Film Co., Ltd. using the light-sensitive material, developing solution and fixing solution used in Example 1. The running conditions were such that a sample of large paper size (50.8 × 61.0 cm) half-exposed in one day was used for 16 samples.
Run 1 sheet, run 6 days and rest 1 day
Six rounds were performed. The sample for photographic evaluation was exposed in the same manner as in Example 1. The replenishing amount of the fixing solution during the running was 1.5 times the replenishing amount of the developing solution.

The processing conditions were as follows: developing time = 20 seconds, developing temperature = 35 ° C., fixing temperature = 34 ° C. Table 2 shows the evaluation results.
2 is shown.

[0249]

[Table 22]

The image forming method of the present invention can provide a processing method with less deterioration in ultra-high contrast, practical skill Dmax and halftone dot sharpness even when running with low replenishment.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hirotomo Sasaki 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (5)

[Claims] 1. A silver halide photographic material containing a hydrazine derivative represented by the following general formula (1), wherein at least one of an aminophenol derivative represented by the general formula (I) or (II) is used. An image forming method characterized by processing with a developing solution containing General formula (1) A- (B) _{m In the} formula, A represents a linking group, B represents a group represented by the following general formula (2), and m represents an integer of 2 to 6. The groups represented by a plurality of Bs linked to A may be the same or different. Embedded image In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁₀ represents a hydrogen atom or a block group, and G ₁ represents —CO—, —COCO—, —C (＝ S) —, —SO
_{2 -, - SO -, -} PO (R 30) - group (. R ₃₀ is selected from the same range as the groups defined in R _10, which may be different from R _10), thiocarbonyl or imino, Represents a methylene group. A ₁₀ and A ₂₀ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Embedded image In the general formulas (I) and (II), R ₁ ,
R ₂ , R ₃ , R ₄ , R ₁₁ , R ₂₂ , R ₃₃ , and R ₇₇ are
They may be the same or different and each represents a hydrogen atom or a substituent. In the general formulas (I) and (II),
R _5, R _6, R ₆₆ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. In the general formula (II), Z represents an atomic group consisting of a carbon atom or an oxygen atom capable of forming a 5- or 6-membered condensed heterocycle together with a nitrogen atom and a benzene ring, and m represents 0
Represents an integer from to 4. 2. The image forming method according to claim 1, wherein the developing solution further contains at least one compound represented by the following general formula (A). Embedded image In the general formula (A), R ₇ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. 3. The image forming method according to claim 2, wherein the dihydroxybenzene-based developing agent is not substantially contained. 4. The image forming method according to claim 3, wherein a silver halide photographic material containing a hydrazine derivative as a solid dispersion is used. 5. The image forming method according to claim 3, wherein the developer contains two aminophenol derivatives. However, at least one of the two aminophenol derivatives is an aminophenol derivative represented by the general formula (I) or the general formula (II).