JPH10186598A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method for processing the silver halide photographic sensitive material superior in stability with the lapse of time and resistance to pressure and small in occurrence of silver sludge even in the case of a small replenishing amount for development by developing in the presence of a specified compound. SOLUTION: The silver halide photographic sensitive material provided with at least one silver halide emulsion layer on a support and having a pH of <=6.0 on its surface undergoes development processing in the presence of her compound of formula I in which each of D and E is a -CH= or -C(Ro )= or an N atom; R0 is a substituting; each of I1 -I3 is an H or halogen atom or an optional substituent combining through one of C, N, O, S, and P atoms with the ring, but at least one of I1 , I2 , I3 , and Ro is a -SM group; M is an alkali metal or H atom or an ammonium group; and when only one of E and D is an N atom, E is an N atom and D is a -CH= or -C(Ro )= group and at that time, each of I2 and I3 is not a hydroxy group.

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, and more particularly, to a silver halide photographic light-sensitive material having excellent storage stability and pressure resistance. The present invention relates to a method for processing a silver halide photographic light-sensitive material which generates little sludge.

[0002]

2. Description of the Related Art Generally, in the development processing of photosensitive materials,
From the viewpoints of speed, simplicity, and handling, an automatic developing machine (hereinafter referred to as an automatic developing machine) is often used.
In recent years, the demand for low replenishment and speeding up of development processing has been increasing, but to meet these demands,
One measure is to increase the activity of the developer. In the processing of black-and-white photosensitive materials, the activity can be increased by increasing the concentration of the developing agent, but the deterioration due to air oxidation is remarkable.
Also, reducing the thickness of the photosensitive material (for example, the protective layer) is effective for rapid processing.

[0003] By the way, the use of sulfite to prevent the deterioration of the developer has been known for a long time. In particular, if an attempt is made to reduce the replenishment amount from the viewpoint of environmental protection as in recent years, the air oxidation of the developer proceeds more and it becomes difficult to maintain the performance. Therefore, a large amount of 0.3 mol / liter or more of sulfite is used. Although it is necessary to use it, sulfite dissolves silver halide, so that silver is eluted from the photosensitive material as a silver sulfite complex in the developing solution. The silver complex is reduced in the developing solution and gradually adheres and accumulates on the developing tank and the roller. This is called silver stain or silver sludge, which adheres to the photosensitive material to be processed to stain the image or contaminate the automatic developing machine itself. Therefore, it is necessary to periodically clean and maintain the equipment.

[0004] As a method of reducing such silver stains, as described in JP-A-56-24347 and JP-A-8-6215, a method of reducing silver ions eluted in a developer is disclosed. A method of adding a compound that suppresses the reduction of silver ions to silver is known. However, in order to obtain a sufficient silver stain prevention effect with these materials, it is necessary to increase the amount of the compound to be added, which leads to low sensitivity, softening (lower gamma), lowering of the practical density (Dmax), Significant effect on photographic properties such as increase in fog. These evils are
This is particularly remarkable in a super-high contrast material containing a hydrazine compound.

On the other hand, in photographic light-sensitive materials, the film surface pH is adjusted to be low for various purposes. For example, JP-A-7-104413 and JP-A-8-220670 disclose that the surface pH of a photosensitive material is adjusted to 5.8 or less or 6.0 or less for the purpose of improving stability over time. In addition, Japanese Patent Publication No. 7-82217 and Japanese Patent Application Laid-Open No. 6-86659 disclose a method of reducing the film surface pH to 5.8 or less and the use of an acidic polymer in order to suppress the occurrence of black spots in a photosensitive material containing a hydrazine nucleating agent. Have been.

[0006]

As described above, lowering the pH of the film surface is effective in preserving the silver halide photographic material over time and preventing the occurrence of black spots during processing. Since it is effective for improvement, the film thickness of the photographic light-sensitive material can be reduced, which is an effective means for rapid processing and for reducing the replenishment amount of the developing solution. Further, softening caused by the silver stain preventive agent is also prevented, which is preferable. However, the amount of silver eluted into the developing solution increases during the developing process, and the silver stain is deteriorated.

Accordingly, it is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material which is hard, has excellent stability over time and pressure resistance, and generates little silver sludge even with a small amount of developing replenishment. It is in.

[0008]

The present invention has been attained by the following. That is, (1) a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support and having a film surface pH of 6.0 or less is imagewise exposed and then developed. A processing method for a silver halide photographic light-sensitive material, wherein development processing is carried out in the presence of the compound of the formula (I) during processing.

[0009]

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In the general formula (I), D and E each represent a —CH ＝ group, a —C (R ₀ ) ＝ group or a nitrogen atom, wherein R ₀ represents a substituent. L _1, L ₂ and L ₃ are each a hydrogen atom, a halogen atom or a carbon atom, a nitrogen atom, an oxygen atom, a substituent bonded to the ring at any of a sulfur atom and a phosphorus atom, L ₁ ~L ₃ may be the same or different. However, at least one of L ₁ , L ₂ , L ₃ and R ₀ has a —SM group (M is an alkali metal atom, a hydrogen atom or an ammonium group). When only one of E and D represents a nitrogen atom, E represents a nitrogen atom and D represents a -CH = group or a -C ( _R0 ) = group,
In this case, L ₂ and L ₃ do not represent a hydroxy group. (2) The method for processing a silver halide photographic material as described in (1) above, wherein at least one hydrazine compound is contained in at least one of the silver halide emulsion layer and the other hydrophilic colloid layer. . (3) The method for processing a silver halide photographic material as described in (1) or (2) above, wherein the silver halide photographic material contains an acidic polymer. (4) The method for processing a silver halide photographic light-sensitive material as described in any one of (1) to (3) above, wherein the replenishing amount of the developer is 320 cc or less per 1 m ^{2 of the} photographic material. (5) The photograph according to any one of the above (1) to (4), wherein the developing agent of the developer is substantially free of hydroquinone and comprises a compound represented by the following general formula (II): Processing method of photosensitive material.

[0011]

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In the general formula (II), Ra and Rb each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group or an alkylthio group. P and Q are a hydroxy group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group,
Represents an alkyl group, an alkoxy group or a mercapto group, or P and Q are bonded to form a 5- to 7-membered group, together with two vinyl carbon atoms substituted with Ra and Rb and a carbon atom substituted with Y. Represents the group of atoms necessary to form a ring. Y represents ＝ O or ＮN-Rc. Here, Rc represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the formula (I) will be described in detail. Specific examples of the substituent other than the hydrogen atom represented by L ₁ , L ₂ and L ₃ and the substituent represented by R ₀ include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). An alkyl group (including an aralkyl group, a cycloalkyl group, an active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (eg, a 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 , A hydroxy group, an alkoxy group (an ethyleneoxy group or a propyleneoxy group Containing repeating group containing), an aryloxy group, heterocyclic oxy group,
Acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing Heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonium, oxamoylamino, (alkyl or aryl) sulfonyluleido, acylureido, acylsulfamoylamino, nitro, mercapto, (alkyl, aryl or heterocycle) thio, (alkyl or aryl) ) A sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a group containing a phosphoric amide or a phosphoric ester structure, and the like. can give.

These substituents may be further substituted with these substituents. Incidentally, E is D is a carbon atom by a nitrogen atom (-CH = group or -C (R ₀₎ = group) for representing, never L _2, L ₃ represents a hydroxy group.

The substituents other than the hydrogen atom represented by L ₁ , L ₂ and L ₃ and the substituent represented by R ₀ are more preferably a substituent having ₀ to 15 carbon atoms, such as a chlorine atom or an alkyl group. ,
Aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, carboxy group or salt thereof, cyano group, alkoxy group, aryloxy group, acyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, Hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, nitro group, mercapto group, (alkyl, aryl or hetero Ring) a thio group, a sulfo group or a salt thereof, and a sulfamoyl group, more preferably
Alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, carboxy group or a salt thereof,
An alkoxy group, an aryloxy group, an acyloxy group, an amino group, an (alkyl, aryl or heterocycle) amino group, a hydroxyamino group, an N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, an acylamino group, a sulfonamide group, A ureido group, a thioureido group, a sulfamoylamino group, a mercapto group, an (alkyl, aryl or heterocycle) thio group, a sulfo group or a salt thereof, and most preferably an amino group, an alkyl group, an aryl group, an alkoxy group, an aryl group An oxy group, an alkylamino group, an arylamino group, an alkylthio group, an allylthio group, a mercapto group, a carboxy group or a salt thereof, a sulfo group or a salt thereof.

In the general formula (I), L ₁ , L ₂ , L ₃ and R ₀ may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring or an aromatic ring is condensed. .

In the general formula (I), at least one of L _{1 to} L ₃ and R ₀ has a —SM group. M represents an alkali metal atom, a hydrogen atom or an ammonium group.
Here, the alkali metal atom is specifically Na, K, L
i, Mg, Ca, etc., which exist as counter cations of -S-. M is preferably a hydrogen atom, an ammonium group, Na ⁺ or K ⁺ , and particularly preferably a hydrogen atom.

Among the compounds of the general formula (I), the compounds represented by the following general formulas (A) and (B) are preferred.

[0019]

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In the general formula (A), each of R _{1 to} R ₄ is a hydrogen atom, a halogen atom, or any of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom bonded to the ring. And represents a substituent, which is the same as L ₁ , L ₂ and L _{3 in} formula (I), and the preferred range thereof is also the same. However, R ₁ and R ₃ do not represent a hydroxy group. R _{1 to} R ₄ may be the same or different, but at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom or an ammonium group.

In the general formula (A), at least one of R _{1 to} R ₄ is a —SM group, and more preferably, at least two of R _{1 to} R ₄ are a —SM group. When at least two of R _{1 to} R ₄ are —SM groups, preferably, R ₄ and R ₁ , or R ₄ and R ₃ are —SM groups.

In the present invention, among the compounds represented by the general formula (A), the compounds represented by the following general formulas (A-1) to (A-3) are particularly preferred.

[0023]

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In the general formula (A-1), R ₁₀ represents a mercapto group, a hydrogen atom, or an arbitrary substituent, and X represents a water-soluble group or a substituent substituted with a water-soluble group. In Formula (A-2), Y ₁ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₂₀ represents a hydrogen atom or an arbitrary substituent. In Formula (A-3), Y ₂ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₃₀ represents a hydrogen atom or an arbitrary substituent. Where R ₁₀ and Y ₁
Does not represent a hydroxy group.

Next, the compounds represented by formulas (A-1) to (A-3) will be described in more detail. In the general formula (A-1), R ₁₀ represents a mercapto group, a hydrogen atom or any substituent. Here, the arbitrary substituents include the same substituents as those described as the substituents other than the hydrogen atom in R _{1 to} R ₄ of the general formula (A). Preferably as R ₁₀ ,
It is a group selected from a mercapto group, a hydrogen atom and the following substituents having 0 to 15 carbon atoms. That is, examples include an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, and an arylamino group.

In the general formula (A-1), X represents a water-soluble group or a substituent substituted with a water-soluble group. Here, the water-soluble group is a sulfonic acid or a carboxylic acid and a salt thereof, a salt such as an ammonio group, or a group containing a dissociable group which can be partially or completely dissociated by an alkaline developer. Has a sulfo group (or a salt thereof),
A carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonium group, a sulfonamide group,
It represents an acylsulfamoyl group, a sulfonylsulfamoyl group, an active methine group, or a substituent containing these groups. In the present invention, the active methine group refers to a methyl group substituted with two electron-withdrawing groups, and specifically, dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, α-acetyl-α-ethoxy And groups such as carbonylmethyl.

The substituent represented by X in the general formula (A-1) is
The above-mentioned water-soluble group, or a substituent substituted with the above-mentioned water-soluble group, and the substituent is a substituent having 0 to 15 carbon atoms, such as an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, Aryloxy group, heterocyclic oxy group, acyloxy group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, sulfamoylamino group, (alkyl, aryl or Heterocycle) thio group,
(Alkyl, aryl) sulfonyl group, sulfamoyl group, amino group and the like, preferably an alkyl group having 1 to 10 carbon atoms (particularly a methyl group substituted with an amino group), an aryl group, an aryloxy group, an amino group, (Alkyl,
(Aryl or heterocycle) amino group, (alkyl, aryl or heterocycle) thio group and the like.

Among the compounds represented by the general formula (A-1), more preferred are the compounds represented by the following general formula (A-1-a).

[0029]

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In the formula (A-1-a), R ₁₁ represents R _{10 in the} general formula (A-1)
And the preferred range is also the same. R ₁₂ , R ₁₃
May be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Provided that at least one of R ₁₂ and R ₁₃ has at least 1
It has two water-soluble groups. Here, the water-soluble group includes a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonium group,
Represents a sulfonamide group, an acylsulfamoyl group, a sulfonylsulfamoyl group, an active methine group, or a substituent containing these groups, preferably a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), Group,
Examples include groups such as an amino group.

R ₁₂ and R ₁₃ are preferably an alkyl group or an aryl group. When R ₁₂ and R ₁₃ are an alkyl group, the alkyl group is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferably, the substituent is a water-soluble group, particularly a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group or an amino group. When R ₁₂ and R ₁₃ are an aryl group,
As the aryl group, a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms is preferable. As the substituent, a water-soluble group, particularly a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, Or an amino group is preferred. When R ₁₂ and R ₁₃ represent an alkyl group or an aryl group, they may combine with each other to form a cyclic structure. Further, a saturated hetero ring may be formed by a cyclic structure.

In the general formula (A-2), Y ₁ represents a water-soluble group or a substituent substituted with a water-soluble group;
X is synonymous. In the general formula (A-2), the water-soluble group represented by Y ₁ or a substituent substituted with a water-soluble group is more preferably an active methine group or the following group substituted with a water-soluble group, Group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl group, and aryl group. More preferably, Y ₁ is an active methine group or an amino group (alkyl, aryl or heterocycle) substituted with a water-soluble group, wherein the water-soluble group is a hydroxy group, a carboxy group or a salt thereof, or a sulfo group. Or a salt thereof is particularly preferred.

Y₁Particularly preferably as hydroxy
Group, carboxy group (or salt thereof), or sulfo group
(Or a salt thereof) substituted with (alkyl, aryl,
Or heterocycle) amino group, and -N (R_{twenty one})
(R_{twenty two}) Group. Where R_{twenty one}, R _{twenty two}Respectively
R of the general formula (A-1-a)₁₂, R₁₃Is synonymous with
The preferred range is also the same.

In the general formula (A-2), R ₂₀ represents a hydrogen atom or an arbitrary substituent, wherein the optional substituent is the same as those described for R _{1 to} R _{4 in} the general formula (A). The same is mentioned. R ₂₀ is preferably a hydrogen atom or a group selected from the following substituents having 0 to 15 carbon atoms. That is, a hydroxy group, an amino group, an alkyl group,
Examples thereof include an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a hydroxylamino group. Most preferably, R ₂₀ is a hydrogen atom.

In formula (A-3), Y ₂ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₃₀ represents a hydrogen atom or any substituent. Y ₂ and R ₃₀ in the general formula (A-3) are Y ₁ and the general formula (A-2) in the general formula (A-2), respectively.
R ₂₀ has the same meaning as that of R _20, and the preferred range is also the same.

Next, the general formula (B) will be described in detail. R _{5 to} R ₇ in the general formula (B) are represented by the general formula (A)
Have the same meanings as R _{1 to} R ₄ , and their preferred ranges are also the same. Further, among the compounds represented by the general formula (B), the compound represented by the general formula (B-1) is particularly preferable.

[0037]

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In formula (B-1), R ₅₀ has the same meaning as R _{5 to} R _{7 in} formula (B), and more preferably X in formulas (A-1) to (A-3). It is a water-soluble group as defined for Y ₁ and Y ₂ or a group substituted with a water-soluble group. In addition, the general formula (B-
Most preferred among the compounds of 1) are compounds represented by the general formula (B-1-a).

[0039]

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In the general formula (B-1-a), R ₅₁ and R ₅₂ have the same meanings as R ₁₂ and R _{13 in the} general formula (A-1-a), and the preferred range is also the same.

The following are specific examples of the compound represented by formula (I) of the present invention, but needless to say, the present invention is not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

Embedded image The amount of the compound represented by the general formula (I) is 1
0.01-10 mmol, preferably 0.1-5 per liter
Millimoles. Also, when added to photosensitive materials,
1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol Ag, preferably 1 × 10 ⁻⁵ mol / mol Ag
× 10 ^{-4 to} 5 × 10 ^-4 mol / mol Ag.

The “film surface pH” in the present invention is 1 cm ²
Add 0.05cc of water on the measurement surface of
This is a value measured using a silver chloride flat composite electrode after leaving the sample for 10 minutes in an atmosphere of RH or higher. Specific examples of the flat electrode include a pH meter manufactured by Toa Denpa Kogyo KK. The membrane surface pH in the present invention is 6.0 or less, preferably 5.0 to 5.
7 When the content is within the above range, it is effective for the storage stability of the silver halide light-sensitive material over time, the prevention of black spots during processing, and the pressure resistance.

The acid for adjusting the pH of the film surface used in the present invention may be either an organic acid or an inorganic acid, such as citric acid,
Acids such as phthalic acid, citric acid ester, salicylic acid and phosphoric acid are preferred. Preferred acidic polymers are those containing an acidic group having a pKa of 9 or less (or a precursor group that gives such an acidic group by hydrolysis).
More preferably, higher aliphatic acids such as oleic acid described in U.S. Pat. No. 2,983,606, acrylic acid, methacrylic acid or maleic acid described in U.S. Pat. No. 3,362,819. And its partial esters or acid anhydrides; French Patent 2,290,6
A copolymer of acrylic acid and an acrylate ester disclosed in U.S. Pat. No. 99,383, and U.S. Pat. No. 4,139,383 and Research Disclosure No.
16102 (1977). Others
U.S. Pat. No. 4,088,493, JP-A-52-1537
No. 39, No. 53-1023, No. 53-4540, No. 53-4541, No. 53-4542 and the like. The content of the acidic polymer is not particularly limited as long as it is an amount which gives the film surface pH, 500 mg / m ² or less, in particular 1 to 300 mg / m ² is preferred. The following are specific examples of the acidic polymer.

[0048]

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In the processing method of the present invention, the developer is substantially free of hydroquinone, and the compound represented by the general formula (II) is used as a developing agent. It is necessary to use a sulfite as a preservative. This is preferable from the viewpoint of preventing silver contamination.

Hereinafter, the general formula (II) will be described in detail. In the general formula (II), Ra and Rb each represent a hydroxy group or an amino group (as a substituent, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-butyl group,
Includes those having a hydroxyethyl group or the like as a substituent. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (Such as a methoxycarbonylamino group), a mercapto group,
Represents an alkylthio group (eg, methylthio group, ethylthio group). Preferred examples of Ra and Rb include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy, hydroxyalkyl, carboxyl, carboxyalkyl, sulfo, sulfoalkyl, amino, aminoalkyl,
Represents an alkyl group, an alkoxy group, a mercapto group,
Or, P and Q represent an atom group necessary to form a 5- to 7-membered ring together with two vinyl carbon atoms substituted by Ra and Rb and a carbon atom substituted by Y. .
Specific examples of the ring structure include -O-, -C (Rd) (Re)-,
-C (Rf) =, -C (= O)-, -N (Rg)-, -N
= And are combined. Where Rd, Re, R
f and Rg each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group or a sulfo group may be mentioned as a substituent), a hydroxy group or a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring and a uracil ring. And as an example of a preferred 5- to 7-membered ring,
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azasiloxhexenone ring,
A uracil ring can be mentioned.

Y is a group composed of ＯO or ＮN-Rc. Here, Rc is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl, ethyl), an acyl group (eg, acetyl), a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl) or a carboxyalkyl group. Represents a group (for example, carboxymethyl, carboxyethyl).

Specific examples of the compound represented by formula (II) are shown below, but the present invention is not limited thereto.

[0055]

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[0056]

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[0057]

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Among them, preferred is ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid).

The ascorbic acids used in the developer used in the present invention include an endiol type (Endiol), an enaminol type (Enaminol), an endamine type (Endiamin), a thiol enol type (Thiol-Enol) and an enamine thiol type (E
namin-Thiol) is generally known as a compound. Examples of these compounds are described in U.S. Pat. No. 2,688,549 and JP-A-62-237443. Methods for synthesizing these ascorbic acids are also well known, and are described, for example, in Tsukio Nomura and Hirohisa Omura, "Reducton Chemistry" (Uchida Lao Tsuruhoshinsha 1969). The ascorbic acids used in the present invention can be used in the form of an alkali metal salt such as a lithium salt, a sodium salt and a potassium salt.

The general range of the amount of the ascorbic acid of the general formula (II) is as follows.
10 ^-3 mol to 1 mol, particularly preferably 10 ^-2 mol to 0.1 mol.
5 moles.

The developer used in the present invention preferably contains 1-phenyl-3-pyrazolidone or a derivative thereof or a p-aminophenol derivative as an auxiliary agent. The most preferred combination is a combination of an ascorbic acid derivative and a p-aminophenol derivative.

1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone and the like. N-methyl-p is used as the p-aminophenol developing agent used in the present invention.
-Aminophenol, p-aminophenol, N- (β
-Hydroxyphenyl) -p-aminophenol, N-
(4-hydroxyphenyl) glycine, o-methoxy-p
There are-(N, N-dimethylamino) phenol, o-methoxy-p- (N-methylamino) phenol and the like, among which N-methyl-p-aminophenol, or Japanese Patent Application Nos. 8-70908 and 8-70908. The aminophenols described in 8-70935 are preferred.

The ascorbic acid derivative developing agent is usually 0.1%.
It is preferably used in an amount of from 0.5 to 1.0 mol / l. Particularly preferably, it is in the range of 0.1 to 0.5 mol / liter. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 to 1.0 mol / liter, more preferably 0.1 to 0.5 mol. /
It is preferable to use the liter and the latter in an amount of 0.2 mol / l or less, more preferably 0.1 mol / l or less.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like.
If a large amount of sulfite is added, it causes silver contamination in the developing solution. Especially preferably, it is 0.1 mol / liter or less.

The silver halide emulsion for use in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and may be silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide, silver iodobromide. However, silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride are preferable. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but a cubic is preferred. The average grain size of the silver halide is preferably from 0.1 μm to 0.7 μm, more preferably from 0.1 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100. It is preferable that the expressed coefficient of variation is 15% or less, more preferably 10% or less and the particle size distribution is narrow. In the silver halide grains, the inside and the surface layer may have a uniform phase or may be different. Further, a localized phase having a different halogen composition may be provided inside or on the surface of the grain.

The photographic emulsion used in the present invention is P. Glafk
ides Chimie et Physique Photographique (Paul Mo
ntel, 1967), Photographic Em by GF Dufin
ulsion Chemistry (The Forcal Press, 1966), V.
Making and Coating Photograph by L. Zelikman et al
ic Emulsion (The Forcal Press, 1964) and the like.

That is, any of an acidic method and a neutral method may be used, and the method of reacting a soluble silver salt with a soluble halide salt may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. Is also good. 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,
No. 55-77737. 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.

In 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,
No. 36890, as described in No. 52-16364, a method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, British Patent No. 4,242,445, JP-A-55-158124. It is preferable to use the method of changing the concentration of the aqueous solution as described to grow the solution quickly within a range not exceeding the critical saturation.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium, ruthenium, osmium and iridium in order to achieve high contrast and low fog. Is preferred. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, more preferably in the range of 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, per mol of silver. Two or more of these metals may be used in combination. These metals can be uniformly contained in silver halide grains, and are disclosed in JP-A-63-29603 and JP-A-2-3062.
As described in JP-A Nos. 36, 3-167545, 4-76534, 6-110146, and Japanese Patent Application No. 4-68305, they can be contained in the particles with a distribution.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III) complex salt, pentachloroacolodium (III) complex salt, tetrachlorodia Examples thereof include a chromium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaammine rhodium (III) complex salt, and a trizalatrodium (III) complex salt. These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of a rhodium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg KCl, NaCl, KBr, NaBr, etc.)
Can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ^-8 mol to 5 × 10 ^-6 mol, particularly preferably 5 × 10 ^-8 mol to 1 × 1 mol per mol of silver halide.
0 ^-6 mol. 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. .

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042 and JP-A-1-285941.
, 2-20852, 2-20855, etc. in the form of a water-soluble complex salt. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] ^-n where M represents Ru, Re or Os, and n is 0, 1,
Represents 2, 3 or 4. In this case, the counter ion is not important and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands, and the like.

Examples of specific complexes used in the present invention are shown below, but the present invention is not limited to these. [ReCl ₆ ] ^-3 [ReBr ₆ ] ^-3 [ReCl ₅ (NO)] ^-2 [Re (NS) Br ₅ ] ^-2 [Re (NO) (CN) ₅ ] ^-2 [Re (O) ₂ ( CN) ₄ ] ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂ O) ₂ ] ^-1 [RuCl ₅ (H ₂ O)] ^-2 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS) ] ^-2 [Ru (CO) ₃ Cl ₃ ] ^-2 [Ru (CO) Cl ₅ ] ^-2 [Ru (CO) Br ₅ ] ^-2 [OsCl ₆ ] ^-3 [OsCl ₅ (NO)] ^-2 [ Os (NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (O) ₂ (CN) ₄ ] ^-4

The addition amount of these compounds is as follows.
1 × 10 per mole^-9Mol ~ 1 x 10 ^-FiveMolar range preferred
And particularly preferably 1 × 10^-8Mol ~ 1 x 10^-6Mole
It is. The addition of these compounds was
At the time of manufacture of the emulsion and at each stage before coating the emulsion.
Can be carried out.
It is preferably incorporated into silver halide grains.

In order to add these compounds into silver halide grains by adding them during silver halide grain formation, a metal complex powder or an aqueous solution dissolved together with NaCl and KCl is added to the aqueous solution during grain formation. A method in which silver halide grains are added to a salt or a water-soluble halide solution, or are added as a third solution when a silver salt and a halide solution are simultaneously mixed, and silver halide grains are prepared by a three-solution simultaneous mixing method; Alternatively, there is a method in which a required amount of an aqueous solution of a metal complex is charged into a reaction vessel during particle formation. Especially powder or NaCl, KCl
Is preferable to add an aqueous solution dissolved together with the above to a water-soluble halide solution. For the addition to the particle surface, a required amount of an aqueous solution of a metal complex can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

Various compounds can be used as the iridium compound used in the present invention, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium, and pentachloronitrosyliridium. These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid) is used. Etc.) or a method of adding an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.). Instead of using water-soluble iridium, it is also possible to add and dissolve another iridium-doped silver halide grain during silver halide preparation.

The silver halide grains in the present invention may be doped with another heavy metal salt. In particular, K ₄ [Fe (CN) ₆ ] and K ₄
Doping of a metal hexacyanoide complex such as [Ru (CN) ₆ ] and K ₃ [Cr (CN) ₆ ] is advantageously performed. Further, the silver halide grains used in the present invention may contain metal atoms such as cobalt, nickel, palladium, platinum, gold, thallium, copper, and lead. The metal is 1 × per mole of silver halide.
It is preferably from 10 ^-9 to 1 × 10 ^-4 mol. Further, in order to incorporate the metal, a metal salt in the form of a single salt, a double salt, or a complex salt can be added at the time of preparing particles.

The silver halide emulsion of the present invention is preferably chemically sensitized. 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, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, and sulfur sensitization and selenium sensitization Method, tellurium sensitization method, gold sensitization method and the like are preferable.

The sulfur sensitization used in the present invention is usually carried out by
Add a yellow sensitizer and keep the emulsion at a high temperature of 40 ° C or more.
It is performed by stirring for a while. Public sulfur sensitizer
Known compounds can be used, for example, in gelatin
In addition to the sulfur compounds contained in, various sulfur compounds,
For example, thiosulfates, thioureas, thiazoles, rhodani
And the like can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. Addition of sulfur sensitizer
The amount depends on the pH, temperature and the size of silver halide grains during chemical ripening.
Changes under various conditions such as
10 per mole ^-7-10^-2Mole, more preferably
10^-Five-10^-3Is a mole.

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. As unstable selenium compounds, JP-B-44-15748, JP-B-43-13489, JP-A-2-13097,
Compounds described in JP-A-2-2229300 and JP-A-3-21798 can be used. In particular, the general formula (VII
It is preferable to use the compounds represented by I) and (IX).

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 silver halide emulsion
It can be tested by the method described in No. 6739. Specifically, U.S. Patent Nos. 1,623,499, 3,320,069,
No. 772,031, British Patent No. 235,211 and No. 1,121,496,
No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,
No. 958, Japanese Patent Application No. 2-333819, No. 3-53693, No. 3-31598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem.S.
oc.Chem.Commun.) 635 (1980), ibid 1102 (1979), ibid 6
45 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin.
Trans.) 1,2191 (1980), edited by S. Patai, edited by The Chemistry of Organ, Selenium and Tellurium
ic Serenium and Tellunium Compounds), Vol1 (1986),
The compounds described in Vol. 2 (1987) can be used.
In particular, the general 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, etc., but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

The noble metal sensitizer used in the present invention includes gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees 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. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added by the method described in European Patent Publication No. EP293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (e.g., those having different average grain sizes, different halogen compositions, different crystal habits, different chemical habits, Those with different conditions) may be used in combination.

The light-sensitive material of the present invention preferably contains at least one hydrazine compound in order to obtain a super-high contrast image. Hereinafter, the hydrazine compound (derivative) used in the present invention will be described.

In the present invention, the compound of the general formula (I) described in Japanese Patent Application No. 6-47961 can be used. Specifically, compounds represented by I-1 to I-53 described in the same specification are used. The following hydrazine derivatives are also preferably used. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. It is a compound represented by the general formula (I) described in JP-B-6-93082.
Compounds 1-38 listed on the page. Compounds represented by formulas (4), (5) and (6) described in JP-A-6-230497, specifically, compound 4- described on pages 25 and 26 of the same publication. 1 to compound 4-10, compounds 5-1 to 5-42 described on pages 28 to 36, and compound 6 described on pages 39 and 40.
1 to 6-7. Compounds represented by formulas (1) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the same publication.
7) and 2-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same publication. It is a compound represented by (Chemical Formula 1) described in JP-A-6-313951.
Compounds described on page 5 to page 5. A compound represented by the general formula (I) described in JP-A-7-5610, specifically from page 5 to
Compounds I-1 to I-38 described on page 10. 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. General formula (H) and general formula (H) described in JP-A-7-104426
Compounds represented by a), 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, which is 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. ), 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. Japanese Patent Application 7-19
Compounds represented by the general formula (1) described in No. 1007, specifically, compounds D-1 to D-55 described in the same publication.

Examples of the hydrazine derivative preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

[Table 4]

[0091]

[Table 5]

[0092]

[Table 6]

[0093]

[Table 7]

[0094]

[Table 8]

[0095]

[Table 9]

[0096]

[Table 10]

The hydrazine nucleating agent may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in such as. 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, by a method known as a solid dispersion method, a powder of a hydrazine derivative is put into water using a ball mill, a colloid mill,
Alternatively, it can be dispersed and used by ultrasonic waves.

The hydrazine nucleating agent may be added to the silver halide emulsion layer or any other hydrophilic colloid layer on the silver halide emulsion layer side with respect to the support. It is preferably added to the layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent is preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, more preferably from 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, per mol of silver halide.
X10 ^{-5 to} 5 × 10 ^-3 mol is most preferred.

When a hydrazine nucleating agent is contained in the light-sensitive material, it is preferable to contain a nucleation accelerator. Examples of the nucleation accelerator include amine derivatives, onium salts, disulfide derivatives, and hydroxymethyl derivatives.

Examples are listed below. JP-A-7-77783
No. 4, pp. 48-37, specifically 49
Compounds A-1) to A-73) described on pages p. JP-A-7-
Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in No. 84331, 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, compounds of Na-1 to Na-22 described on pages 16 to 20 of the same publication And compounds of Nb-1 to Nb-12. The general formula (1), 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) described in Japanese Patent Application No. 7-37817. )), Specifically, the compounds of 1-1 to 1-19, the compounds of 2-1 to 2-22 described in the same specification,
Compounds of 3-1 to 3-36, compounds of 4-1 to 4-5, 5
-1 to 5-41, 6-1 to 6-58 and 7-1 to 7-38.

Further specific compounds include the following compounds.

[0102]

Embedded image

The nucleation accelerator may be a suitable water-miscible organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used. 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 may be added to the silver halide emulsion layer or any other hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. It is preferably added to the layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator is 1 × 10 ^-6 ~2 × 10 ^-2 mol per mol of silver halide is preferred, more preferably 1 × 10 ^-5 ~2 × 10 ^-2 mol, 2 ×
Most preferably, it is 10 ^-5 to 1 × 10 ^-2 mol.

In the present invention, it is preferable to contain a polymer latex having an active methylene group in order to increase the film strength of the light-sensitive material. Specifically, JP-A-2-
No. 103536, page 18, lower left line, line 12 to lower left line, line 20; a polymer latex having an active methylene group represented by the general formula (I) described in Japanese Patent Application No. 8-13592. , Specifically the compound I- described in the same specification.
1 to I-16, 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 are preferably used. .

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 oxonol 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 17643 IV-A (December 1978, p.23) and Item 1831X (August 1979).
p.437) or in the literature cited.

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)
Japanese Patent Laid-Open No. 60-162 discloses an argon laser light source.
No. 247, compounds of (I) -1 to (I) -8,
Compounds I-1 to I-228 described in JP-A-2-48653 and compounds I-1 to I-28 described in JP-A-4-330434.
-13, a compound of Example 1 to Example 14 described in U.S. Pat. No. 2,161,331, a compound of West German Patent 936,
Nos. 1 to 7 described in JP-A-071; B) Helium-neon lasers, red semiconductor lasers, and LED light sources are described in JP-A-54-18726.
Compound No. 38, 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, JP-B-55-3981.
No. 8, dyes 1 to 20 described in JP-A No. 62-284343.
And the compounds of I-1 to I-37 described in
No. 287338, compounds of I-1 to I-34,
C) Japanese Unexamined Patent Publication No. Sho 59-1 for an infrared semiconductor laser light source
Compounds I-1 to I-12 described in JP-A-91032, compounds I-1 to I-22 described in JP-A-60-80841, and compounds I-1 to I- described in JP-A-4-335342.
Compound No. 29 and compounds I-1 to I-18 described in JP-A-59-192242, and D) Tungsten and xenon light sources for plate making cameras are disclosed in JP-A-55-450.
(1) to (1) represented by general formula [I] described in No. 15
Compound (9) described in Japanese Patent Application No. 7-346193 (I-1)
To I-97, the compounds of 4-A to 4-S, the compounds of 5-A to 5-Q, and the compounds of 6-A to 6-T described in JP-A-6-242546 are advantageously selected. Is done.

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 Disclosur.
e) Vol. 176, Volume 17643 (December 1978) No. 23
Section IV on page IV, or the aforementioned JP-B-49-25500,
43-4933, JP-A-59-19032, and 59-19032.
192242.

Two or more sensitizing dyes may be used in combination. 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 US 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 a dispersion to an emulsion,
No. 23389, No. 44-27555, No. 57-220
As disclosed in No. 91 or the like, a dye is dissolved in an acid,
A method in which the solution is added to the emulsion, or an acid or base is added to the emulsion as an aqueous solution in the presence of an acid or a base, U.S. Pat.
No. 822,135, 4,006,025, etc., a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to an emulsion as disclosed in -102733, 58-1051
No. 41, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion,
As disclosed in JP-A-51-74624, a method in which a dye is dissolved using a compound that causes red shift, and the solution is added to an emulsion can also be used. Also,
Ultrasound can also be used for the solution.

The sensitizing dye may be added to the silver halide emulsion at any stage of the emulsion preparation which has been found to be useful. For example, U.S. Pat. Nos. 2,735,766 and 3,628,960,
Nos. 4,183,756 and 4,225,666
JP-A-58-184142 and JP-A-60-19674.
As disclosed in the specification of No. 9, etc., the timing before the step of forming silver halide grains and / or before desalting, the timing during and / or after desalting and before the start of chemical ripening, As disclosed in the specification of JP-A-58-113920 and the like, at any time during the process immediately before or during chemical ripening, or after chemical ripening and before coating, before the emulsion is coated. May be added. Also,
U.S. Pat. No. 4,225,666, JP-A-58-762.
As disclosed in the specification such as No. 9, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle formation step and during the chemical ripening step or after the completion of the chemical ripening, The compound may be added in portions such as before aging or during the process and after completion, or may be added by changing the kind of compound to be added and the combination of compounds.

The amount of the sensitizing dye to be added depends on the shape and size of the silver halide grains, the halogen composition, the method and degree of chemical sensitization,
Depending on the type of antifoggant, silver halide 1
It can be used in an amount of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol. For example, a silver halide grain size of 0.2 to
In the case of 1.3 μm, the surface area of silver halide grains is 1 m ^2.
Per, 2 × 10 ^-7 to 3.5 × preferably amount of 10 ^-6 mol, more preferably the addition amount of 6.5 × 10 ^-7 to 2.0 × 10 ^-6 mol.

As a binder for the silver halide emulsion layer and other hydrophilic colloid layers, gelatin is preferably used, but other hydrophilic colloids can be used, and they can be used in combination with gelatin.
For example, gelatin derivatives, graft polymers of gelatin and other high molecular compounds, proteins such as albumin, casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl Use of various kinds of synthetic hydrophilic high molecular substances such as mono- or copolymers of alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

In the present invention, the coating amount of gelatin as a binder is such that the amount of gelatin in the entire hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g / m ² or less (preferably 1.0 to 2.5 g / m ² ). ² ) The total gelatin content of the entire hydrophilic colloid layer on the side having the silver halide emulsion layer and the total hydrophilic colloid layer on the opposite side is 7.0 g / m ² or less, preferably 2.0 g / m ² or less. ６6.0 g / m ² .

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, compound (III)-
1-25 compounds. A compound represented by the general formula (I) described in JP-A-1-18832 and having substantially no absorption maximum in the visible region. Specifically, compounds I-1 to I-1 described in the publication
A compound of I-26. 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-2-103536, page 18, lower left
The polymer latex described from the 12th line to the lower left 20th line of the same page. Japanese Patent Application Laid-Open No. 2-103536, from page 17, lower right, line 19
An antifoggant described in the fourth line on the upper right of page 18. JP-A-2-103536
Matting agents, slip agents, and plasticizers described on page 19, top left, line 15 to page 19, top right, line 15. Hardeners described in JP-A-2-103536, page 18, upper right line, line 5 to line 17, upper right 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.

Conductive substances described in JP-A-2-18542, page 2, lower left, line 13 to page 3, upper right, line 7 Specifically, the metal oxides described on page 2, lower right line 2 to the lower right line 10 of the same publication, and compounds P-1 to P-2 described in the same publication
-7 conductive polymer compound. JP-A-2-103536 No. 17
Water-soluble dyes described in the first line from the lower right of the page to the upper right line of the same page.
General formula (FA) and general formula (FA) described in Japanese Patent Application No. 7-350753.
1) A solid disperse dye represented by the general formula (FA2) or (FA3). Specifically, compounds F1-F described in the publication
34, (II-2) to (II-2) described in JP-A-7-152112.
4), (III-5) to (III-1) described in JP-A-7-152112.
8), (IV-2) to (IV-) described in JP-A-7-152112.
7).

JP-A-2-94638 and Japanese Patent Application No. 3-185773
The solid disperse dye described in the above item. Surfactants described in JP-A-2-12236, page 9, upper right, line 7 to lower right, line 3; PEG-based surfactants described in JP-A-2-103536, page 18, lower left line, line 4 to lower left line, line 7; Fluorinated surfactants described in JP-A-3-39948, page 12, lower left line, line 6 to page 13, lower right line, line 5; Specifically, compound VI described in the publication
-1 to VI-15 compounds.

Redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-247816.
Preferably, a redox compound represented by the general formula (R-1), the general formula (R-2) or the general formula (R-3) described in the publication. Specifically, compounds R-1 to R-68 described in the publication
Compound. From the first line on the lower right of page 3 of JP-A-2-18542
Binder on line 20.

As the support used in the present invention, for example, polyester films such as baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, for example, polyethylene terephthalate, and JP-A-7-234478. Mention may be made of the described polystyrene films having a syndiotactic structure. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is 80.
To 150%, more preferably 90 to 1%.
It is in the range of 40%. The swelling ratio of the hydrophilic colloid layer is determined by measuring the thickness (d ₀ ) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic material, and distilling the silver halide photographic material at 25 ° C. Immerse in water for 1 minute,
The swelled thickness (Δd) was measured, and the swelling ratio (%) = Δd ÷
It is determined by the formula of d ₀ × 100.

The processing agents such as the developing solution and the fixing solution, the processing method and the like in the present invention are described below. There are no particular restrictions on the developing agents used in the developing solution (hereinafter, both the developing start solution and the developing replenisher are collectively referred to as a developing solution) used in the present invention, but dihydroxybenzenes, ascorbic acid derivatives, hydroquinone mono- It preferably contains a sulfonate, and may be used alone or in combination. Further, from the viewpoint of developing ability, a combination of a dihydroxybenzene or an ascorbic acid derivative with 1-phenyl-3-pyrazolidone or a combination of a dihydroxybenzene or an ascorbic acid derivative with a p-aminophenol is preferable.

Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone. Hydroquinone is particularly preferred. Further, ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

The developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone and the like. Examples of the p-aminophenol-based developing agent include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. However, among them, N-methyl-p-aminophenol is preferable.

The dihydroxybenzene-based developing agent is usually 0.1%.
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.23 mol / l to 0.5 mol / l. It is preferred to use the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is usually used in an amount of 0,1.
It is preferably used in an amount of from 01 mol / l to 0.5 mol / l, more preferably from 0.05 mol / l to 0.3 mol / l. When a combination of an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone or p-aminophenol is used, the ascorbic acid derivative may be used in an amount of 0.01 to 0.5 mol / l, 1-phenyl-3-pyrazolidone or p-aminophenol. The aminophenols are preferably used in an amount of from 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto.

As the buffer used in the developer for developing the light-sensitive material in the present invention, carbonates, JP-A-62-186
No. 259, saccharides (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt) described in JP-A-60-93433 , Potassium salt) and the like, and preferably carbonate and boric acid. The amount of buffer, especially carbonate used, is preferably
It is at least 0.01 mol / l, especially 0.05 to 1.5 mol / l.

The preservatives that can be used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde sodium bisulfite, and the like. Sulfite is used in an amount of 0.2 mol / L or more, particularly 0.3 mol / L or more. However, if added in an excessive amount, it causes silver contamination in the developing solution.
The upper limit is desirably 1.2 mol / l. Particularly preferably, it is 0.35 to 0.7 mol / liter.

As a preservative of the dihydroxybenzene-based developing agent, a small amount of the above 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 in terms of molar ratio to the dihydroxybenzene-based developing agent, and particularly preferably 0.05 to 0.12.
It is in the range of ~ 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Examples of the additives other than those described 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 (eg, 3- (5-
Sodium mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventive agents.

Further, in addition to the compound of the present invention, a mercapto compound, an indazole compound, a benzotriazole compound or a benzimidazole compound may be contained as an antifoggant or a black pepper (black pepper) 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-thiol,
Chlorobenzotriazole, bromobenzotriazole, nitrobenzotriazole, methylbenzotriazole and the like can be mentioned. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.05 to 2 mmol, per liter of 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. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As aminopolycarboxylic acids, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycolethertetraacetic acid, 1
, 2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others JP-A-52-25632, JP-A-55-67747. ,same
Compounds described in JP-B-57-102624 and JP-B-53-40900 can be exemplified.

Examples of the organic phosphonic acid include, for example, US Pat. Nos. 3,214,454 and 3,794,591 and West German Patent Publication 222736.
No. 9, etc., hydroxyalkylidene-diphosphonic acid and Research Disclosure Vol. 181, Item 18170
(May, 1979). Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like.
JP-A-57-208554, 54-61125, 55-29883, 5
Compounds described in JP-A-6-97347 and the like can be mentioned.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726, 53-42730, and 54-1211.
No. 27, No. 55-4024, No. 55-4025, No. 55-126241, No. 55-65955, No. 55-65956, and compounds described in the aforementioned Research Disclosure 18170 and the like.

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, in addition to the compound of the general formula (I) as a silver stain inhibitor in a developer, a triazine having at least one mercapto group (for example, trimercaptotriazine, dimercaptotriazine, mercaptotriazine, 2-hydroxy-4 , 6-dimercaptotriazine and the like 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-7-248587) And the like pyrazines (eg, 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-triazine) The same pyridazine (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), the same triazole (eg, mercaptotriazole, Dimercaptotriazole, 1-methyl-2,5-dimercaptotriazole, etc.), the same thiadiazole (for example, 2-mercaptothiadiazole, 2,5-dimercaptothiadiazole and the like), compounds described in JP-A-7-175177,
Polyoxyalkyl phosphonates described in U.S. Pat. No. 5,457,011 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. Further, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

The preferred pH of the developer is from 9.0 to 10.8, particularly preferably from 9.5 to 10.8. 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 cations in the developer, 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, the molar ratio of potassium ion to sodium ion in the developer is preferably 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.

[0142] replenishing amount of developer per photosensitive material 1 m ² 33
0 ml or less is preferable, and 325 to 50 ml is more preferable. A good effect of the present invention can be obtained even with such a low replenishing amount, which is preferable from the viewpoints of reduction of waste liquid amount and environmental hygiene. 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 agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent to be used can be changed as appropriate, but is generally from about 0.7 to about
3.0 mol / l.

The fixing solution of the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, aluminum lactate, and aluminum gluconate. These are preferably contained at 0.01 to 0.15 mol / l as the 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 desired, preservatives (for example, sulfites, bisulfites, metabisulfites and the like) may be used in the fixing treatment agent at 0.015%.
Mol / l or more, preferably 0.02 mol / l ~
0.3 mol / l), pH buffer (eg acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate,
0.1 mol / L to 1 mol / L, preferably 0.2 mol / L to 0.7 mol / L of phosphoric acid, succinic acid, adipic acid, and the like, and compounds having an aluminum stabilizing ability or a water softening ability (for example, gluconic acid, iminodi Acetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediamine Acetic acid, nitrilotriacetic acid and their derivatives and their salts, saccharides, boric acid, etc.
1 mol / l to 0.5 mol / l, preferably 0.1 mol / l
005 mol / l to 0.3 mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can also be contained. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6840. Known antifoaming agents are used. You can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-Hei 6-1994
No. 308681, alkyl- and allyl-substituted thiosulfonic acids and salts thereof, and JP-B-45-35754, 58-1
Nos. 22535 and 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.
It can contain the mercapto compound described in 1-4739, 1-159645 and 3-101728, the mesoionic compound described in 4-17039, and the thiocyanate.

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 7.0. The pH of the fixing solution is raised by the processing mixed with the developing solution. In this case, the pH is 6.0 or less, preferably 5.7 or less for the hardened fixing solution, and 7.0 or less, preferably 6.7 or less for the non-hardened fixing solution.

The replenishment rate of the fixing solution is 50 per m ² of the photosensitive material.
0 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml. 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. By regenerating, the replenishment rate of the fixing solution can be reduced to 200 ml / m ² or less. As a playback device, for example, Fuji Hunt Re
claim R-60 and others. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

When the developing and fixing agent in the present invention is a liquid agent, 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 solidified, the solid processing agent will be described below. The solid preparation in the present invention may be in a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.). 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 separate 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 2, line 48 to column 3, line 13 can be referred to.

In the case of forming a plurality of layers, components that do not react even if they come into contact with each other may be sandwiched between components that 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, for example, in JP-A-61-259921 and JP-A-4-16841.
Nos. 4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g / cm ³
Is preferred, especially the tablet is preferably 1.0 to 5.0 g / cm ³ ,
Granules preferably 0.5 to 1.5 g / cm ^3.

As a 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,
4-32837, 4-78848, 5-93991, JP-A-4-855
No. 33, No. 4-85534, No. 4-85535, No. 5-134362, No. 5-
197070, 5-204098, 5-224361, 6-138604
No., No. 6-138605, and Japanese Patent Application No. 7-89123 can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt coagulation, 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, JP-A-6-242585 to JP-A-6-242588, JP-A-6-247432, JP-A-6-247448, Japanese Patent Application No.
No. 5-30664, JP-A-7-5664, 7-5666 to 7-5669 can also be made into a foldable shape as disclosed in, for reducing the storage space of waste packaging material preferable. 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. Examples of these methods include a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a method disclosed in
A method of dissolving with a dissolving apparatus having a dissolving part and a part for storing a finished liquid as described in 7-235499 and replenishing from the stock part, JP-A-5-119454, JP-A-6-19102
No. 7-261357 No. 7-261357, a method of introducing and dissolving and replenishing a processing agent into the circulating system of an automatic developing machine, processing according to the processing of photosensitive material with an automatic developing machine with a built-in dissolution tank Although there is a method of adding and dissolving the agent, any other known method can be used. Also, the input of the processing agent may be performed manually, or may be automatically opened by a melting device or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498, and may be automatically input, The latter is preferred in terms of working environment. More specifically, there are a method of breaking through the outlet, a method of peeling, a method of cutting out, a method of pushing out, and methods described in JP-A-6-19102 and JP-A-6-95331.

The photosensitive material which has been subjected to the development and fixing is then washed or stabilized (hereinafter, unless otherwise specified, the washing including the stabilization is called washing, and 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 amount of replenishment is generally but about 17 liters to about eight liter photosensitive material 1 m ^2, can also be carried out in less replenishing rate. 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 washing with a small amount of water is performed, it is more preferable to provide a squeezing roller and a crossover roller washing tank described in JP-A-63-18350 and JP-A-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, and the replenishing amount of washing is preferably 200 to 50 ml per 1 m ² of the photosensitive material. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, a scale preventing means may be provided in the washing step. Known means can be used as the scale prevention means, and is not particularly limited, but a method of adding a fungicide (so-called scale prevention agent), a method of applying electricity, a method of irradiating ultraviolet rays or infrared rays or far infrared rays, 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 antifungal agent is not particularly limited, and a known one can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-
Mercaptopyridine-N-oxide, etc.)
They may be used alone or in combination. As a method of energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16280,
The method described in No. 4-18980 can be used.

In addition, a known water-soluble surfactant or antifoaming agent may be added to prevent water bubble unevenness and stain transfer. Further, a dye adsorbent described in JP-A-63-163456 may be provided in a washing system to prevent contamination by a dye eluted from the light-sensitive material.

A part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. 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), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain a biochemical oxygen demand. Water (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining or forming a filter using a polymer with affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment to lower the silver concentration in the wastewater by adding a compound to the mixture to precipitate silver and filtering the precipitate by a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, JP-A-2-201357 and JP-A-2-132435.
Baths containing the compounds described in JP-A Nos. 1-102553 and 46-44446 may be used as the final bath of the light-sensitive material.
If necessary, this stabilizing bath also contains an ammonium compound, Bi, A
metal compounds such as l, optical brighteners, various chelating agents, film p
H regulators, hardeners, bactericides, sunscreens, alkanolamines and surfactants can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths and the stabilizing agents may be solid agents as in the above-mentioned developing and fixing 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. In addition, these waste liquids are, for example, Japanese Patent Publication No. 7-83867, US5439
It is also possible to condense or liquefy or solidify using a concentrating device such as that described in No. 560 and then dispose.

In order 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 oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,554,971 and the like, and are simply referred to as roller transport type automatic developing machines 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, the dry-to-dry
~ 160 seconds, development and fixing time is 40 seconds or less,
Preferably, the temperature of each solution is 6 to 35 seconds, and the temperature of each liquid is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. Washing temperature and time are 0 to
Preferably, the temperature is 50 seconds or less at 50 ° C. 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.
Heat roller drying and drying by far infrared rays as disclosed in JP-A Nos. 4-15534, 5-2256 and 5-289294 may be used, and a plurality of methods may be used in combination.

[0170]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of emulsion (1 liquid) 750 ml of water 20 g of gelatin 20 g of sodium chloride 20 mg of 1,3-dimethylimidazolidin-2-thione 10 mg of sodium thiosulfonate (2 liquid) 300 ml of water 150 g of silver nitrate (3 liquid) 300 ml of water 34 g of sodium chloride Potassium bromide 32 g Potassium hexachloroiridate 0.25 mg Ammonium hexabromorhodate 0.06 mg Yellow blood salt 5 mg

One solution kept at 38 ° C. and pH 4.5 was added with 2
The liquid and the three liquids were each added in an amount corresponding to 90% with stirring over a period of 20 minutes to form 0.16 μm core particles. Subsequently, the following liquids 4 and 5 were added over 8 minutes, and the remaining 10% of the liquids 2 and 3 were added over 2 minutes to grow to 0.18 μm. further,
0.15 g of potassium iodide was added to terminate the particle formation.

(Liquid 4) Water 100 ml Silver nitrate 50 g (Liquid 5) Water 100 ml Sodium chloride 14 mg Potassium bromide 11 mg Potassium ferrocyanide 5 mg

Thereafter, water was washed by flocculation according to a conventional method, and 45 g of gelatin was added. pH
5.6, adjusted to pAg 7.5, sodium thiosulfonate 10 mg, sodium thiosulfinate 3 mg, sodium thiosulfate 1 mg and triphenylphosphine selenide 1
mg and chloroauric acid (5 mg) were added, and the mixture was subjected to chemical sensitization at 55 ° C. so as to obtain optimum sensitivity, and 1,3,3a, 7-tetraazaindene (200 mg) was added as a stabilizer. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average particle diameter of 0.18 μm was obtained (coefficient of variation: 9%).

To the obtained emulsion, 200 mg of the sensitizing dye (a) was added to 1 mol of Ag, 5 g each of KBr and KI, and hydroquinone as a stabilizer, the following compounds (b), (c) and (d). ) For 5 g, 0.2
g, 0.2 g and 1 g were added.

[0175]

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Further, the compound 2b was used as a nucleating agent in the form of 1
× 10 ^-4 mol, 0.2 g of the compound A-6 as a nucleation accelerator was added. 0.4 g of sodium dodecylbenzenesulfonate, polyethyl acrylate latex and colloidal silica of 0.01 μm in an amount corresponding to a gelatin binder ratio of 30% each, a dispersion of polyethyl acrylate at 150 mg / m ² , methyl acrylate and 2
-Acrylamide-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate latex copolymer (weight ratio 88: 5: 7) were added to 150
mg / m ² , core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37/63), shell: styrene / 2-acetoacetoxyethyl methacrylate (weight ratio 84/16), core / shell ratio = 50 / 50) to 1
50 mg / m ² and 2-bis (vinylsulfonylacetamido) ethane as a hardener were added in an amount corresponding to a gelatin binder ratio of 4%. Further, as shown in Table 1, the acid was added to adjust the film surface pH.

They were coated on a subbed polyester support having a moisture-proof layer containing vinylidene chloride so that the silver coating amount was 3.2 g / m ² and the gelatin coating amount was 1.4 g / m ² . By changing the type of the sensitizing dye as shown in Table 1,
A sample was prepared. An upper protective layer and a lower protective layer having the following composition, and an undercoat layer having the following composition, were applied thereon.

Upper layer of protective layer Gelatin 0.3 g / m ² Average 3.5 μm silica matting agent 25 mg / m ² Compound (e) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (f) 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (g) 20 mg / m ²

Lower layer of protective layer Gelatin 0.5 g / m ² Compound (h) 15 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ²

UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (i) 40 mg / m ² Compound (j) 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 (k) 40 mg / m ² Compound (l) 20 mg / m ² Compound (m) 90 mg / m ² 1,3-divinylsulfonyl- 2-propanol 60 mg / m ² Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (n) 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 diameter 0.25 μ) 200 mg / m ²

[0183]

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[0184]

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The composition per liter of the concentrated solution of the developer (1) is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-Methylbenzotriazole 0.25 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.35 g Compound of general formula (I) The concentration in the working solution is described in Table 1. Sodium erythorbrate 9.0 g Diethylene glycol 60.0 g pH 10 .7 For use, dilute 2 parts water with 1 part concentrated solution. The pH of the working solution is 10.5.

The following silver stain inhibitor was used for comparison.

[0187]

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The prescription per liter of the concentrated solution of the fixing solution (1) is shown below. Ammonium thiosulfate 360 g Ethylenediamine.tetraacetic acid.2Na.dihydrate 0.09 g Sodium thiosulfate.pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90. 0 g tartaric acid 8.7 g sodium gluconate 5.1 g aluminum sulfate 25.2 g pH 4.85 For use, dilute 2 parts of water to 1 part of the above concentrated liquid. The pH of the working solution is 4.8.

As ammonium thiosulfate (compact), a flake product prepared by a spray-drying method was pressed and compressed by a roller compactor and crushed into amorphous chips of about 4 to 6 mm in size, and was blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 L of both the A agent and the B agent were filled in a foldable container made of high-density polyethylene, and the outlet of the A agent was sealed with an aluminum seal. The mouth of the B agent container was sealed with a screw cap. Japanese Patent Application No. 7-2354 for dissolution and replenishment
No. 99, Japanese Patent Application No. 7-235498, a dissolution replenishing apparatus having an automatic opening mechanism was used.

[Sensitometry] The obtained sample was
Exposure to xenon flash light with an emission time of 10 ⁻⁶ seconds was performed through an interference filter having a peak at 3 nm and a step wedge, and the temperature was reduced to 35 ° C. and 30 ″ using an FG-680AG automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.). The film was processed under development conditions and subjected to sensitometry, and the reciprocal of the exposure amount giving a density of 1.5 was defined as the sensitivity.
The straight line connecting is used as the gradation.

[Evaluation of Storage Property] The sample was left standing at 50 ° C. and 55% for 10 days to perform a forced storage test. The difference in sensitivity from that left at room temperature was ΔS, and was expressed as a percentage.

[Evaluation of Pressure Property] A sample was scratched and developed by applying a load to a diamond needle having a diameter of 0.01 mm system. The load at which fogging started was measured, and the pressure was evaluated.

[Evaluation of Silver Stain] Each sample was exposed to a blackening ratio of 20%, and was set at 100 m ² / day for 10 days at a developing temperature of 35 ° C., a fixing temperature of 34 ° C., and a developing time of 30 seconds. , The replenishment rate of the developing solution and the fixing solution was 160 ml / m ²
After processing with a replenishing rate of 6 L / m ² of washing water, the generation of sludge in the developing tank and on the developing roller was visually observed, and a paper photosensitive material KU-150WP (6 cm × 30) manufactured by Fuji Photo Film Co., Ltd. .3 cm), and the degree of contamination was visually evaluated on a 10-point scale. "10" is the best and "1" is the worst. "10" to "6" are practical,
"5" is poor but practically usable, "4" to "1"
Indicates a level that is not practical.

[0194]

[Table 11]

The sample having a high film surface pH shows relatively good silver stain even when a developer using the silver stain inhibitor used for comparison is used, but the storage stability, the pressure property, and the gradation are poor. Inferior,
It is understood that the film surface pH is low, and that all of the storability, the pressure property, and the silver stain can be satisfied only when processed with a developer using the silver stain inhibitor of the present invention.

Example 2 In Example 1, the sensitizing dye was changed to the following compound (o), and the following compound (p) was added as a supersensitizer to the following compound (p).
A sample was prepared in exactly the same manner except that mg / mol Ag was added.
In sensitometry, evaluation was conducted in exactly the same manner as in Example 1 except that the interference filter was changed to one having a peak at 780 nm, and the superiority of the present invention was similarly shown as shown in Table 2.

[0197]

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[0198]

[Table 12]

Example 3 An experiment similar to that of Example 1 was carried out using a solid developer (developer (2)).
And using a solid fixing agent (fixing solution (2))
Similar results were obtained. The compound of the general formula (I) is shown in Table 1.
It was evaluated in the same manner as in the above.

The composition of the solid developer (developer (2)) is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (raw powder) 63.0 g Sodium sulfite (raw powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) 40.0 g

Diethylenetriamine / pentaacetic acid 2.0 g to be briquetted together 2.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g General formula (I The compound in the working solution is described in Table 1. 3- (5-Mercaptotetrazol-1-yl) sodium benzenesulfonate 0.1 g Sodium erythorbate 6.0 g Potassium bromide 6.6 g Dissolve in water Bring to 1 L. pH 10.65

Here, in the form of raw materials, raw powders were used as general industrial products, and beads of alkali metal salts were commercially available. When the raw material was in the form of a briquette, a plate-like material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For minor components, each component was blended before briquetting. 10 L of the above treating agent was filled in a high-density polyethylene foldable container, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, a dissolution and replenishment device having an automatic opening mechanism disclosed in Japanese Patent Application Nos. 7-235499 and 7-235498 was used.

The composition of the solid fixing agent (fixing solution (2)) is shown below. Agent A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (raw powder) 19.0 g Sodium metabisulfite (raw powder) 18.0 g Anhydrous sodium acetate (raw powder) 42.0 g B Agent (Liquid) Ethylenediamine / tetraacetic acid / 2Na / 2-hydrate 0.03 g Citric anhydride 3.7 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water and add 50 mL I do. The A agent and the B agent were dissolved in water to make 1 L. pH 4.8

Example 4 A similar result was obtained by using the following developer in the same experiment as in Example 1. The compound of the general formula (I) was used in the same manner as in Table 1. As shown in Table 3, when this developing solution was used, silver stain was particularly good.

[0205]

[Table 13]

<Developer Composition> Diethylenetriamine-5-acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium bicarbonate 25 g Sodium erythorbate 45 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-methyl Benzotriazole 0.00 4 g 1-phenyl-5-mercaptotetrazole 0.02 g Compound of general formula (I) The concentration in the working solution is described in Table 1. Sodium sulfite 2 g Water was added to 1 liter, and the pH was 9. Adjust to 7.

Example 5 In Example 1, the same result was obtained by performing the same processing using the FG-680AS manufactured by the same company as the automatic processing machine and setting the transport speed of the photosensitive material to a linear speed of 1500 mm / sec. Was.

[0208]

According to the present invention, a method for processing a silver halide photographic light-sensitive material having high contrast, excellent stability over time and pressure resistance, and little generation of silver sludge even with a small development replenishment amount can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/305 G03C 5/305 5/31 5/31

Claims (5)

[Claims] 1. A support having at least one light-sensitive silver halide emulsion layer on a support, and having a film surface pH of the light-sensitive material.
A method for processing a silver halide photographic light-sensitive material, comprising, after imagewise exposing a silver halide photographic light-sensitive material of 6.0 or less, and performing development processing in the presence of a compound of the formula (I) during development processing. Embedded image In the general formula (I), D and E each represent -CH =
Group, —C (R ₀ ) = group or a nitrogen atom, wherein R ₀
Represents a substituent. L _1, L ₂ and L ₃ are each a hydrogen atom, a halogen atom or a carbon atom, a nitrogen atom, an oxygen atom, a substituent bonded to the ring at any of a sulfur atom and a phosphorus atom, L ₁ ~L ₃ may be the same or different. However, at least one of L ₁ , L ₂ , L ₃ and R ₀ has a —SM group (M is an alkali metal atom, a hydrogen atom or an ammonium group). When only one of E and D represents a nitrogen atom, E represents a nitrogen atom and D represents a —CH ＝ group or a —C (R ₀ ) ＝ group, and in this case, L ₂ and L ₃ represent hydroxy. It does not represent a group. 2. The method according to claim 1, wherein at least one hydrazine compound is contained in at least one of the silver halide emulsion layer and the other hydrophilic colloid layer.
The method for processing a silver halide photographic light-sensitive material described in the above. 3. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material contains an acidic polymer. 4. The replenishing amount of the developing solution is 3 per 1 m ^{2 of} the photosensitive material.
4. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing speed is 20 cc or less. 5. The photographic light-sensitive material according to claim 1, wherein the developing agent of the developer is substantially free of hydroquinone and comprises a compound represented by the following general formula (II). Material treatment method. Embedded image In the general formula (II), Ra and Rb each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group or an alkylthio group. P and Q each represent a hydroxy, hydroxyalkyl, carboxyl, carboxyalkyl, sulfo, sulfoalkyl, amino, aminoalkyl, alkyl, alkoxy or mercapto group, or P and Q Are bonded together with the two vinyl carbon atoms substituted by Ra and Rb and the carbon atom substituted by Y to 5
Represents an atom group necessary to form a 7-membered ring. Y =
Represents O or = N-Rc. Here, Rc represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group.