JPH07104426A - Silver halide photographic material and image formation - Google Patents

Abstract

PURPOSE:To suppress the change of sensitivity and soft tone formation and prevent the generation of fog and black tint by allowing a silver halide emulsion layer and/or the contiguous layer to contain hydrazine derivatives and allowing a hydrophilic colloid layer to contain the nucleus formation accelerating agent. CONSTITUTION:Hydrazine derivatives are contained in a silver halide emulsion layer on a supporting body and/or the contiguous layer, and the nucleus formation accelerating agent is contained in the hydrophilic colloid layer on the opposite side, having the supporting body interposed. Preferably, in the hydrophilic colloid layer on the opposite side to the silver halide emulsifier layer, the compound represented by the formula I or the compound represented by the formula II is contained. In the formula I, each of X and Y is a nitrogen atom, or =C(R12)-, and at least one between X and Y is a nitrogen atom. R11 is a hydrogen atom, lower alkyl group, nitro group, etc., and R12 represents a hydrogen atom, lower alkyl group, mercapto group, etc. In the formula II, R21-R23 represent a hydrogen atom, substituted or nonsubstituted alkyl group having the number of carbon atoms of 1-12, alkenyl group, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and an image forming method thereof, and more particularly to a silver halide photographic light-sensitive material for printing plate making and a developing method thereof.

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this step, a technique by infectious development has been used as a method for reproducing an ultrahigh contrast image. Examples of the lith type silver halide photographic light-sensitive material used for infectious development include those having an average particle size of about 0.2 μm or less, a narrow particle distribution and a well-shaped silver chloride content of at least 50 mol% or more. Silver halide emulsions are commonly used.

Such a lith-type silver halide photographic light-sensitive material can be processed with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type infectious developer to obtain an image with high contrast and high resolution.

However, the lith-type developer has a drawback that it is easily oxidized by air, and its preservability is extremely poor, so that it is difficult to keep the quality constant during continuous development processing.

Therefore, as a method for rapidly obtaining a high-contrast image without using such a developing solution, for example, a silver halide photographic light-sensitive material containing a hydrazine derivative as described in JP-A-56-106244. A method of treating a material with an alkaline developer is disclosed. According to this method, the preservability of the developing solution is good, rapid processing is possible, and an ultrahigh contrast image can be easily obtained. However, in this method, in order to fully exhibit the high contrast property of the hydrazine derivative, the hydrazine derivative had to be treated with a developer having a pH of 11.0 or more.

In a strongly alkaline developing solution having a pH of 11.0 or more, when the developing solution comes in contact with air, the developing agent is significantly oxidized. Although more stable than the lith developer described above, there are many cases in which a super-high contrast image cannot often be obtained due to the oxidation of the developing agent.

In order to compensate for such drawbacks, JP-A-63-29751
No. 1, JP-A-1-179939, the same 1-179940, U.S. Pat.
No. 354 discloses a silver halide photographic light-sensitive material containing a hydrazine derivative capable of increasing the tone even with a developer having a relatively low pH of less than 11.0 and accelerating nucleation.

On the other hand, the black-and-white silver halide photographic light-sensitive material is
Generally, after exposure, most are processed using an automatic processor. Then, at that time, it is general that a certain amount of developing solution proportional to the area of the light-sensitive material is replenished and processed so as to obtain stable photographic performance. Conventionally, in order to obtain a high contrast image as described above, in order to prevent deterioration of the developing solution capacity due to fatigue of the processing solution during continuous processing and air oxidation, processing is usually performed while replenishing with 300 ml or more of a developing replenisher solution per 1 m ^2. I've been However, in recent years, there has been an urgent need to reduce the amount of developing waste liquid with increasing concern about the environment. for that reason,
When a high-sensitivity light-sensitive material as described above is processed in a small amount of replenishing replenishing amount of 200 ml or less per 1 m ² and continuously processed by an automatic processor, stable development processing cannot be performed, and sensitivity fluctuation and softening are caused by continuous processing. However, there is a problem in that an unexposed portion of a light-sensitive material using a hydrazine derivative is liable to cause a failure such as a so-called black spot after development.

When processing is performed using an automatic processor,
Conventionally, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic processor until it comes out of the drying zone is
It usually took 90 seconds or more, but in recent years, it has been demanded to shorten the development processing time by increasing the number of printing points and the working time, and the total processing time is 60 seconds or less. For continuous processing with an automatic processor under various conditions,
The above failures are more likely to occur.

[0010]

In order to solve the above problems, the first object of the present invention is, firstly, to use a photosensitive material capable of increasing the tone even when the pH of the developer is less than 11.0, and It is an object of the present invention to provide a silver halide photographic light-sensitive material and an image forming method in which fluctuations in sensitivity and softening hardly occur even when continuously processed while being replenished. A second problem is a silver halide photographic light-sensitive material which has less fog and black spots even if it is continuously processed while replenishing the developer with an automatic developing machine in a light-sensitive material which is hardened even in a developer having a pH of less than 11.0. An object is to provide an image forming method.

[0011]

The above object of the present invention can be achieved by the following method.

1. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. A silver halide photographic light-sensitive material having at least one nucleation accelerator in at least one hydrophilic colloid layer opposite to the silver halide emulsion layer. material.

2. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. After exposure of a silver halide photographic light-sensitive material having a pH of 1 to ² , the replenishment amount of the developer is ² per 1 m ² of the light-sensitive material in an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is performed while replenishing at a ratio of not more than 00 ml, at least one nucleation accelerator is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. Image forming method.

3. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. A silver halide photographic light-sensitive material having the formula (1), wherein at least one hydrazine derivative is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer.

4. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. After exposure of a silver halide photographic light-sensitive material having a pH of 1 to ² m2, the amount of replenishment of the developer is 1 m ² with an automatic processor containing a developer having a pH of less than 11.0.
An image forming method in which development is performed while replenishing at a ratio of 200 ml or less, wherein at least one hydrazine derivative is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. Forming method.

5. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. In the silver halide photographic light-sensitive material having the formula (1), at least one compound represented by the general formula [1] is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. And a silver halide photographic light-sensitive material.

6. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. After exposure of a silver halide photographic light-sensitive material having a pH of 1 to ² m2, the amount of replenishment of the developer is 1 m ² with an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is performed while replenishing at a ratio of 200 ml or less, at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer is represented by the general formula [1] (Formula 1). An image forming method comprising at least one compound.

7. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. In the silver halide photographic light-sensitive material having the following formula, at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer is selected from the general formulas [2], [3] and [4] A silver halide photographic light-sensitive material containing at least one compound selected from the following.

8. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. After exposure of a silver halide photographic light-sensitive material having a pH of 1 to ² m2, the amount of replenishment of the developer is 1 m ² with an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is performed while replenishing at a ratio of 200 ml or less, in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer, the above-mentioned general formula [2],
An image forming method comprising at least one compound selected from [3] and [4] (Chemical Formula 2).

9. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. A silver halide photographic light-sensitive material having a polyhydroxybenzene compound in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer.

10. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. After exposure of a silver halide photographic light-sensitive material having a pH of 1 to ² , the replenishment amount of the developer is ² per 1 m ² of the light-sensitive material in an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is carried out while replenishing at a ratio of not more than 00 ml, an image forming method wherein a polyhydroxybenzene compound is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. Method.

11. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. A silver halide photographic light-sensitive material containing at least one redox compound capable of releasing a development inhibitor by being oxidized in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. A silver halide photographic light-sensitive material characterized by the above.

12. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. After exposure of a silver halide photographic light-sensitive material having a pH of 1 to ² , the replenishment amount of the developer is ² per 1 m ² of the light-sensitive material in an automatic processor containing a developer having a pH of less than 11.0.
A redox compound capable of releasing a development inhibitor by being oxidized in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer in an image forming method in which development is performed while replenishing at a ratio of not more than 00 ml. At least 1
An image forming method characterized by containing a seed.

13. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. A silver halide photographic light-sensitive material having at least one compound selected from water-soluble chlorides, bromides and iodides in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. A silver halide photographic light-sensitive material characterized by being

[0025] 14. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one hydrophilic colloid layer is provided on the opposite side of the silver halide emulsion layer sandwiching the support. After exposure of a silver halide photographic light-sensitive material having a pH of 1 to ² m2, the amount of replenishment of the developer is 1 m ² with an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is performed while replenishing at a ratio of 200 ml or less, at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer is selected from water-soluble chloride, bromide and iodide. An image forming method comprising one compound.

The present invention will be specifically described below.

First, as the hydrazine derivative used in the present invention, a compound represented by the following general formula [H] is used.

[0028]

[Chemical 3]

The general formula [H] will be described in detail below.

In the formula, the aliphatic group represented by A is preferably one having 1 to 30 carbon atoms, and particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group,
Examples thereof include a benzyl group and the like, which further include suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfoxy group,
Sulfonamide group, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [H] is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A in the general formula [H] is preferably a monocyclic or condensed ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, such as a pyrrolidine ring, Examples thereof include an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring.

Particularly preferred as A is an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents are an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms, substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
Group), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxyl group, a phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

Further, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group has 8 carbon atoms.
Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group, an alkylphenoxy group and the like, which are relatively inert to the above photographic properties.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B is specifically an acyl group (eg formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc.), alkylsulfonyl groups (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (eg methanesulfinyl etc.), an arylsulfinyl group (benzenesulfinyl etc.), a carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), an alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.), an aryloxycarbonyl Groups (eg phenoxycarbonyl etc.), sulfamoyl groups (eg dimethylsulfamoyl etc.), sulfinamoyl groups (eg methylsulfur) Finamoyl etc.), an alkoxysulfonyl group (eg methoxysulfonyl etc.), a thioacyl group (eg methylthiocarbonyl etc.), a thiocarbamoyl group (eg methylthiocarbamoyl etc.), an oxalyl group (the general formula [Ha] will be described later) or a heterocyclic group. (Eg, pyridine ring, pyridinium ring, etc.).

B in the general formula [H] represents A ₂ and the nitrogen atom to which they are attached,

[0039]

[Chemical 4]

May be formed.

R ₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.)

Among the hydrazine compounds used in the present invention, the compounds represented by the following general formula [Ha] are particularly preferable.

[0045]

[Chemical 5]

In the formula, R ₄ represents an aryl group or a heterocyclic group, and R ₅ represents

[0047]

[Chemical 6]

Represents

R ₆ and R ₇ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Alternatively, it represents a heterocyclic oxy group, and R ₆ and R ₇ may form a ring together with an N atom. R ₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. A ₁ and A ₂ represent the same meanings groups as A ₁ and A ₂ in formula (H).

The general formula [Ha] will be described in more detail.

The aryl group represented by R ₄ is preferably a monocyclic ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₄ is preferably a 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, which is a monocyclic ring or a condensed ring. Examples thereof include a ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

Preferred as R ₄ is a substituted or unsubstituted aryl group. Examples of the substituent include those having the same meaning as the substituent of A in the general formula [H].
When the contrast is increased with a developing solution of 1.2 or less, it is preferable to have at least one sulfamide group.

[0054] A ₁ and A _2, A ₁ and A ₂ of the formula H
And a hydrogen atom are the most preferable.

R ₅ is

[0056]

[Chemical 7]

Wherein R ₆ and R ₇ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.),
Alkenyl groups (allyl, butenyl, etc.), alkynyl groups (propargyl, butynyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl) Nyl, quinolidinyl, N, N'-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy , Ethoxy, etc.), alkenyloxy group (allyloxy etc.), alkynyloxy group (propargyloxy etc.), aryloxy group (phenoxy etc.), or heterocyclic oxy group (pyridyloxy etc.), and R ₆ and R ₇ are nitrogen. A ring (piperidine, morpholine, etc.) may be formed together with the atom. R ₈ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.), a heterocycle Group (2,2,
6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl and the like).

Specific examples of the compounds represented by the general formulas [H] and [Ha] are shown below. However, the present invention is not limited to these.

[0059]

[Chemical 8]

[0060]

[Chemical 9]

[0061]

[Chemical 10]

[0062]

[Chemical 11]

[0063]

[Chemical 12]

[0064]

[Chemical 13]

[0065]

[Chemical 14]

[0066]

[Chemical 15]

The method of synthesizing the compound represented by the general formula [H] used in the present invention is described in JP-A Nos. 62-180361 and 62-178246.
No. 63-234245, No. 63-234246, No. 64-90439, JP-A No. 2-37, No. 2-841, No. 2-947, No. 2-120736, No.
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604, 4,994,365, European patent 253,665
No. 333,435, etc. can be referred to.

The amount of the compound represented by the general formula [H] used in the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

In the present invention, the compound represented by the general formula [H] is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer. The hydrazine derivative contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer is also a compound represented by the above general formula [H].

Next, as the nucleation accelerator, the following general formula [N
Examples thereof include those shown in a] or [Nb].

[0071]

[Chemical 16]

In the general formula [Na], R ₁ , R ₂ , R ₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. A ring can be formed by R ₁ , R ₂ and R ₃ . Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a molecular weight of 300 or more is more preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific compounds include those shown below.

[0074]

[Chemical 17]

[0075]

[Chemical 18]

[0076]

[Chemical 19]

[0077]

[Chemical 20]

In the general formula [Nb], Ar represents a substituted or unsubstituted aryl group or heteroaromatic ring. R represents an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have a preferable diffusion resistant group, the molecular weight is preferably 120 or more, particularly preferably 300 or more.

Specific compounds include those shown below.

[0080]

[Chemical 21]

[0081]

[Chemical formula 22]

[0082] The amount of nucleation accelerator of the present invention is preferably from 1 mol of silver halide per 5 × 10 ^-7 ~5 × 10 ^-1 mol, particularly 5 × 10 ^-1 ~1 × 10 ^- It is preferably in the range of ¹ mol.

The nucleation accelerator is also preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the emulsion layer.

Next, the compound represented by the above general formula [1] will be described.

In the above general formula [1], the lower alkyl group represented by R ₁₁ may be linear or branched and has 1 carbon atom.
To 8 and examples thereof include a methyl group, an ethyl group, an iso-propyl group, and a butyl group. The group represented by R ₁₁ is preferably a nitro group.

Specific representative examples of the compound represented by the general formula [1] are shown below.

(1-1) 5-nitroindazole (1-2) 6-nitroindazole (1-3) 5-methylindazole (1-4) 6-methylindazole (1-5) indazole (1-6) 5-chloroindazole (1-7) 5-methylbenzimidazole (1-8) 5-ethylbenzimidazole (1-9) 5-nitrobenzimidazole (1-10) 6-nitrobenzimidazole (1-11) 5 -Chlorobenzimidazole (1-12) Benzimidazole (1-13) 2-Mercapto-benzimidazole (1-14) 2 Mercapto-5-methylbenzimidazole (1-15) Benzotriazole (1-16) 5-methyl benzotriazole (1-17) 5-chloro-benzotriazole formula compound per mol of silver halide 1 × 10 ^-6 ~1 × 10 ^-1 mol represented by [1] Used in amount,
Particularly preferably, it is in the range of 1 × 10 ^{−4 to} 5 × 10 ⁻² mol.
This compound may be added by dissolving it in water or an organic solvent such as methol, ethanol or the like, which is optionally miscible with water, and then adding it to the constituent element.

Next, general formulas [2], [3] and [4] (Formula 2) will be described.

In the general formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ ,
R ₃₂ , R ₃₃ , R ₄₁ and R ₄₂ are a hydrogen atom or a carbon atom of 1 to
12 alkyl groups (eg, methyl, ethyl, propyl, cyclohexyl, dodecyl, etc.), alkenyl groups (eg, allyl, 2-butenyl, etc.), alkoxy groups (eg, methoxy, ethoxy, butoxy, etc.), alkoxycarbonyl groups ( (Eg, methoxycarbonyl, ethoxycarbonyl, etc.), amino groups (eg, amino, methylamino, benzylamino, anilino, 4-methoxyanilino, etc.), aryl groups (eg, phenyl, naphthyl, etc.),
It represents a hydroxy group, a mercapto group, a carboxyl group or a salt thereof, or a halogen atom (eg, fluorine, chlorine, etc.).

The above alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group and aryl group are all substituents (eg halogen, hydroxy, carboxy,
Alkyl, aryl, alkoxy, mercapto, alkoxycarbonyl, etc.).

R ₃₄ and R ₄₃ are a phosphoric acid group or an optionally substituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, hydroxymethyl, hydroxyethyl, etc.)
Represents

Typical examples of the general formula [2] include the following, but the invention is not limited thereto.

[0093]

[Chemical formula 23]

[0094]

[Chemical formula 24]

The following can be mentioned as typical specific examples represented by the general formula [3] or [4], but the present invention is not limited thereto.

(3-1) 6-Amino-purine riboside (3-2) 6-chloro-purine riboside (3-3) 6-hydroxy-purine riboside (3-4) 6-methylamino-purine riboside (3-5) 2 -Amino-6-hydroxy-purine riboside (3-6) 5'-phosphate-6-amino-purine riboside (3-7) 5'-phosphate-6-chloro-purine riboside (3-8) 5'-phosphate -6-Hydroxy-purine riboside (3-9) 5'-phosphate-6-methylamino-purine riboside (3-10) 5'-hydroxymethyl-6-amino-purine riboside (3-11) 5'-methyl-6 -Amino-purine riboside The compounds represented by the general formulas [2], [3] and [4] are preferably used in an amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide. , Particularly preferably 1 × 10 ⁻⁵
It is in the range of 1 × 10 ^-2 mol. As a method of adding this compound, a usual method of adding an additive to a photographic emulsion can be used. For example, the water-soluble compound can be used as an aqueous solution having a suitable concentration, and the water-insoluble or sparingly soluble compound can be dissolved in a suitable organic solvent miscible with water and added to the emulsion as a solution.

The polyhydroxybenzene compound of the present invention is a polyhydroxybenzene compound having two or more substituted or unsubstituted hydroxy groups, preferably the following general formulas [5], [6] and [7]. It is at least one selected from.

[0098]

[Chemical 25]

[Wherein R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ ,
R ₅₆ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group, a carboxylalkyl ester group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a sulfo group,
It represents an amidoalkyl group, an amidophenyl group, an imidoalkyl group, and a nitrile group. ]

[0100]

[Chemical formula 26]

[Wherein R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ ,
R ₆₆ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group, a carboxylalkyl ester group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a sulfo group,
It represents an amidoalkyl group, an amidophenyl group, an imidoalkyl group, and a nitrile group. ]

[0102]

[Chemical 27]

[Wherein R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ and R ₇₆ are each a hydrogen atom, a chlorine atom, a fluorine atom, a sulfo group, an unsubstituted or substituted alkyl group, an alkylamino group, Aryl group, aralkyl group, heterocyclic group,-
Represents O-R ₇₇ or -S-R ₇₇ . R ₇₇ represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. Next, the general formula [5] (Formula 25) will be described.

In the general formula [5], R ₅₁ , R ₅₂ , R ₅₃ , R
₅₄ , R ₅₅ and R ₅₆ are hydrogen atom, halogen atom, carbon number 1
~ 23 alkyl group, C1-23 alkoxy group, carboxyl group, carboxylalkyl ester group, hydroxyalkyl group, hydroxyalkoxyalkyl group, sulfo group, amidoalkyl group, amidophenyl group, imidoalkyl group, nitrile group Represent

The above groups also include those having a substituent. For example, a fluorinated alkyl group or a sulfo group substituted with an alkali metal can be used.

R ₅₃ , R ₅₄ , R ₅₅ and R ₅₆ may form a ring with each other, or may form a dimer while forming a ring.

Next, the above general formula [5] used in the present invention is used.
Representative specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0108]

[Chemical 28]

Specific compounds other than the above are disclosed in JP-A-
There are compound examples 4-7 to 4-12 and 4-15 to 4-20 described in 3-36541, pages 311 (17) to 312 (18).

Next, the general formula [6] (Formula 26) will be described.

In the general formula [6], R ₆₁ , R ₆₂ , R ₆₃ , R
₆₄ , R ₆₅ and R ₆₆ are hydrogen atom, halogen atom, carbon number 1
~ 23 alkyl group, C1-23 alkoxy group, carboxyl group, carboxylalkyl ester group, hydroxyalkyl group, hydroxyalkoxyalkyl group, sulfo group, amidoalkyl group, amidophenyl group, imidoalkyl group, nitrile group Represent

The above groups also include those having a substituent. For example, a fluorinated alkyl group or a sulfo group substituted with an alkali metal can be used.

Next, the above general formula [6] used in the present invention is used.
Representative specific examples of the compound represented by are shown below, but the invention is not limited thereto.

[0114]

[Chemical 29]

Specific compounds other than the above are described in JP-A
2-310555 pp. 363 (17) to 364 (18) include compound examples 4-7 to 4-22 and 4-26 to 28 and 4-31 to 37.

Next, the general formula [7] (Formula 27) will be described.

In the general formula [7], R ₇₁ , R ₇₂ , R ₇₃ , R
₇₄ , R ₇₅ and R ₇₆ are each a hydrogen atom, a chlorine atom, a fluorine atom, a sulfo group, an unsubstituted or substituted alkyl group, an alkylamino group, an aryl group, an aralkyl group, a heterocyclic group, —O—R ₇₇ or — Represents S-R ₇₇ . R ₇₇ represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. Specific examples of the compound represented by the general formula [7] are shown below, but the present invention is not limited to these compounds.

[Exemplified Compounds] 7-1 Hydroquinone 7-2 2-Chloro-hydroquinone 7-3 2-Methoxyhydroquinone 7-4 2-n-Octadecylhydroquinone Specific compounds other than the above are described in JP-A-3-36540. 28
Compound Examples III-2 to 5 (5) to 286 (6)
III-17, III-19 to III-23 and III-26 to III-39.
The amount of the compound of the general formula [5], [6] or [7] contained in the silver halide photographic light-sensitive material of the present invention is as follows, per 1 mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. 5 × 10 ^{-6 to} 5 × 10 ^-1 mol, particularly preferably 5
It is preferably in the range of × 10 ^-5 to 1 × 10 ^-2 mol.

In order to incorporate the compound of the general formula [5] [6] or [7] of the present invention in the hydrophilic colloid layer, the compound of the general formula [5] [6] or [5] [6] or [6] or [7] can be added to an appropriate water and / or organic solvent. 7]
And a method of adding a solution obtained by dissolving a liquid in an organic solvent after dispersing it in a hydrophilic colloid matrix of gelatin or a gelatin derivative, or a method of dispersing and adding it in a latex. .

The addition positions of the compounds represented by the general formulas [1] to [7] in the emulsion manufacturing process are arbitrary positions.
Preferably, it is added after the grain formation and before the coating.

The compound of the general formula [1] is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer, but is contained in the silver halide emulsion layer and / or other hydrophilic layer. May be done.

General formulas [2], [3], [4], [5],
The addition position of the compound of [6] or [7] is also represented by the general formula [1].
Is the same as.

Next, examples of the redox group of the redox compound capable of releasing a development inhibitor by being used in the present invention include hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones and hydrazine. Examples thereof include hydroxylamines, reductones and the like. Hydrazines are preferable as the redox group, and compounds represented by the following general formula [R] are particularly preferable as the redox compound.

[0124]

[Chemical 30]

In the general formula [R], B ₁ and B ₂ are hydrogen atoms, both are hydrogen atoms or sulfonic acid residues, one is a hydrogen atom and the other is a sulfinic acid residue, for example, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group. A group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is −0.5 or more) or — [C (O)] ₁ —R ₀ [R ₀ is preferably carbon Number 30 or less linear, branched or cyclic alkyl group, alkenyl group, aryl group (preferably phenyl group, or phenyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more), alkoxy Group (for example, an ethoxy group), an aryloxy group (preferably a monocyclic group)], etc., and these groups may have a substituent. Those of the lower and the like.
These groups may be further substituted. For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group,
Sulfo group, carboxyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, nitro group,
An alkylthio group, an arylthio group, and the like. B ₁ ,
The sulfinic acid residue represented by B ₂ is specifically described in US Patent
Represents those described in No. 4,478,928.

B ₁ may form a ring by linking _with- (Time) _t- described later.

Hydrogen atoms are most preferred as B ₁ and B ₂ .

Time represents a divalent linking group and may have a timing adjusting function. t represents 0 or 1, and t = 0
In the case of, it means that PUG is directly bonded to V.

The divalent linking group represented by Time is one step from Time-PUG released from the oxidant of the redox mother nucleus, or
It represents a group that releases PUG through further steps of reaction.

The divalent linking group represented by Time is a photographically useful group obtained by the intramolecular ring closure reaction of the p-nitrophenoxy derivative described in, for example, US Pat. No. 2,248,962 (JP-A-54-145135). Releasing PUG); US Pat. No. 4,31
Nos. 0,612 (JP-A-55-53330) and 4,358,252 which release PUG by an intramolecular ring closure reaction after ring cleavage; U.S. Patents 4,330,617, 4,446,216, 4,483,
No. 919, JP-A-59-121328, etc., which releases PUG with the formation of an acid anhydride by the intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or its analogs;
U.S. Patents 4,409,323 and 4,421,845, Research Disclosure No. 21,228 (December 1981), U.S. Patents
4,416,977 (JP-A-57-135944), JP-A-58-209736
No. 58-209738 and the like, which produces quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG; US Pat. No. 4,420,554 Issue (JP-A-57-136640
No. 57,135945, 57-188035, 58-98728.
And a nitrogen-containing heterocycle described in JP-A-57-56837 by electron transfer of a portion having an enamine structure of the nitrogen-containing heterocycle described in JP-A No. 58-209737, etc .; Intramolecular Ring Closure of Oxy Group Generated by Electron Transfer to Carbonyl Group Conjugated with Nitrogen Atom
Those that release PUG; U.S. Pat. No. 4,146,396 (JP-A-52-9)
0932), JP-A-59-93442, JP-A-59-75475 and the like, which release PUG with the formation of aldehydes;
Those releasing PUG with decarboxylation of the carboxyl group described in JP-A-51-146828, JP-A-57-179842, and JP-A-59-104641; having the structure of -O-COOCR ₂ R ₆ -PUG , Releasing PUG with decarboxylation and subsequent formation of aldehydes;
JP-A No. 60-7429, which releases PUG with formation of an isocyanate, PUG by a coupling reaction with an oxidant of a color developing agent described in U.S. Pat.
And the like can be mentioned.

Specific examples of these divalent linking groups represented by Time are described in detail in JP-A No. 61-236549, Japanese Patent Application No. 63-98803, and the like.

The main development inhibitors are mercaptotetrazole derivatives, mercaptotriazole derivatives, mercaptoimidazole derivatives, mercaptopyrimidine derivatives, mercaptobenzimidazole derivatives, mercaptothiadiazole derivatives, mercaptobenzthiazole derivatives, mercaptobenzoxazole derivatives, benztriazole derivatives, and benz. Examples thereof include an imidazole derivative, an indazole derivative, a tetrazole derivative, a tetrazaindene derivative, and a mercaptoaryl derivative.

V represents a carbonyl group, -C (O) C (O)-, sulfonyl group, sulfoxy group, -P (O) (R ₁₄ ) -R ₁ (R ₁ represents an alkoxy group or an aryloxy group. ), An iminomethylene group, and a thiocarbonyl group, and V is preferably a carbonyl group.

The aliphatic group represented by R is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, preferably having 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms. belongs to. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein.

For example, methyl group, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, hexenyl group,
Examples thereof include a pyrrolidyl group, a tetrahydrofuryl group, an n-dodecyl group.

The aromatic group is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O or S atoms, which may be a monocyclic ring or may be another aromatic ring or heterocyclic ring. A condensed ring may be formed with the ring. Preferred as the hetero ring is a 5- to 6-membered aromatic hetero ring, for example, a pyridine ring, an imidazolyl group,
Examples thereof include a quinolinyl group, a benzimidazolyl group, a pyrimidinyl group, a pyrazolyl group, an isoquinolinyl group, a benzthiazolyl group and a thiazolyl group.

R may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio. Group, arylthio group, sulfothio group, sulfinyl group, hydroxy group,
Halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxy group, and a phosphoric acid amide group. Further, in the general formula [R], R or-(Time) _t -PUG is a compound represented by the ballast group or the general formula [R] which is commonly used in the non-moving photographic additives such as couplers. A group that promotes the adsorption of the group on the silver halide may be incorporated.

The ballast group is an organic group which gives a molecular weight sufficient to prevent the compound represented by the general formula [R] from substantially diffusing into another layer or the treatment liquid. It is composed of one or more combinations of heterocyclic groups, ether groups, thioether groups, amide groups, ureido groups, urethane groups, sulfonamide groups and the like.
The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the adsorption-promoting group for silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, and tetrazoline-5-. Thion, 1,2,4-triazoline-
3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione Cyclic thioamide group, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom, the relationship between this and the tautomer And a specific example of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole. , Thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, Azine, nitrogen, such as azaindene, oxygen, sulfur, and 5- to 6-membered nitrogen-containing heterocyclic group comprising a combination of carbon, and the like heterocyclic quaternary salts such as benz imidazolinium the like.

These may be further substituted with appropriate substituents. Examples of the substituent include those mentioned as the substituent of R.

Specific examples of the compound used in the present invention are listed below, but the present invention is not limited thereto.

[0144]

[Chemical 31]

[0145]

[Chemical 32]

[0146]

[Chemical 33]

[0147]

[Chemical 34]

[0148]

[Chemical 35]

[0149]

[Chemical 36]

[0150]

[Chemical 37]

[0151]

[Chemical 38]

[0152]

[Chemical Formula 39]

[0153]

[Chemical 40]

[0154]

[Chemical 41]

[0155]

[Chemical 42]

[0156]

[Chemical 43]

The redox compound used in the present invention can be synthesized by, for example, JP-A Nos. 61-213847 and 62-260153, US Pat. No. 4,684,604, Japanese Patent Application No. 63-98803, and US Pat. No. 3,379,5.
No. 29, No. 3,620,746, No. 4,377,634, No. 4,332,878
JP-A-49-129536, JP-A-56-153336, JP-A-56-153342
No., etc.

The redox compound of the present invention is used in the range of 1.0 × 10 ^-4 mol to 5.0 × 10 ^-2 mol, preferably 1.0 × 10 ^{-5 to} 1.0 × 10 ^-2 mol, per mol of silver halide. .
The redox compound of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving in dimethyl sulfoxide, methyl cellosolve and the like.

In addition, it is dissolved in an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate with an auxiliary solvent such as ethyl acetate or cyclohexanone by a well-known emulsion dispersion method. Alternatively, an emulsified dispersion can be mechanically prepared and used. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The redox compound of the present invention is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer, but it contains a hydrazine nucleating agent-containing photosensitive emulsion layer and / or other hydrophilic colloid layer. It can be contained in the colloid layer.

At least one compound selected from water-soluble chlorides, bromides and iodides according to the present invention will be described. Preferred compounds are alkali metal salts of chlorine, bromine and iodine, such as lithium salts, sodium salts and potassium salts. Other salts useful in the present invention are magnesium, calcium, strontium and ammonium salts. Furthermore, chlorides, bromides and iodides having a molecular weight of up to 350 can be used. Addition amount is 1
It is 10 ^-6 to 10 ^-1 mol per m ² .

In the present invention, a nucleation accelerator, a hydrazine derivative, a compound of the general formula [1], general formulas [2], [3] and [4] are provided in at least one layer on the opposite side of the silver halide emulsion layer. At least one compound selected from the group consisting of polyhydroxybenzene compound, redox compound or water-soluble chloride, bromide and iodide
The compound contains various kinds of compounds, but may be contained in combination. For example, a nucleation accelerator and at least one compound selected from water-soluble chlorides, bromides, and iodides may be added together in at least one layer on the opposite side of the silver halide emulsion layer. The compound of formula [1] may be added together.

The light-sensitive material of the present invention is preferably provided with at least one conductive layer on the support. As a typical method for forming the conductive layer, a water-soluble conductive polymer,
There are a method of forming using a hydrophobic polymer and a curing agent and a method of forming using a metal oxide. For these methods, for example, the methods described in JP-A-3-265842, page (5) to page (15) can be used.

The silver halide emulsion used in the present invention (hereinafter referred to as a silver halide emulsion or simply an emulsion) includes, for example, silver bromide, silver iodobromide, silver iodochloride, chloroodor. Although any of those used in ordinary silver halide emulsions such as silver halide and silver chloride can be used, silver chlorobromide, silver chloride or chloroiodide containing 60 mol% or more of silver chloride is preferable. It is silver bromide.

[(Standard deviation of particle size)] / (average value of particle size)
Monodisperse particles represented by × 100 and having a coefficient of variation of 15% or less are preferable.

In the light-sensitive material of the present invention, the total amount of gelatin on the emulsion layer side is preferably 3.5 g / m ² or less. The emulsion layer side means the side of the layer having a silver halide emulsion with respect to the support,
Includes silver halide emulsion layers and other layers. Other layers include, for example, an emulsion protective layer, an antihalation layer,
A UV absorbing layer, an intermediate layer, a conductive layer and the like can be mentioned. The total amount of gelatin contained in the silver halide emulsion layer and other layers is preferably 3.5 g / m ² or less, particularly preferably 0.5 to 3.0.
It is g / m ² .

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention. For example,
The silver halide photographic emulsion and backing layer used in the present invention include various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, and ultraviolet absorbers. , An anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion of the present invention and the backing layer.

These additives are described in more detail in Research Disclosure Vol. 176 Item / 7643 (December 1978) and Vol. 187 Item / 8716 (November 1979). It is summarized below.

Additive type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic Agent Page 27 As above As a support which can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate,
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass and metal. These supports are subjected to a surface treatment if necessary.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing after exposure by various methods, for example, a commonly used method.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromhydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone and 2,5-dimethylhydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3- Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc., aminophenols (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2 , 4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (tato) If 1
-(p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-
Methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.) alone or Although they can be used in combination, it is preferable to use them in a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes. The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / l.

In the present invention, examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. The sulfite is preferably 0.25 mol / l or more. It is particularly preferably 0.4 mol / l or more.

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a silver sludge inhibitor (for example, JP-B-62-4702, JP-A-03-51844).
No. 04-26838, No. 04-362942, No. 01-319031, etc.), pH buffer (for example, carbonate, phosphate, borate, boric acid, acetic acid, citric acid) , Alkanolamines, etc., dissolution aids (eg polyethylene glycols, their esters, alkanolamines etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.), surface active agents Agents, antifoaming agents, antifoggants (for example, halogens such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example, Ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetate,
Polyphosphate, etc., development accelerator (eg US Pat. No.
2,304,025, compounds described in Japanese Patent Publication No. 47-45541, etc.), hardeners (eg glutaraldehyde or
The bisulfite adduct, etc.), or an antifoaming agent can be added. The pH of the developer is less than 11.0, 9.
It is preferably adjusted to 5 to 10.5.

In the present invention, as a special form of development processing, an activator processing solution which contains a developing agent in a light-sensitive material, for example, an emulsion layer, and processes the light-sensitive material in an alkaline aqueous solution to perform development may be used. . Such a development process, in combination with a thiocyanate silver salt stabilization treatment,
It is often used as one of the methods for rapid processing of a light-sensitive material, and the effects of the present invention can be obtained even when rapid processing is performed with such a processing solution.

As the fixing liquid, those having a generally used composition can be used. The fixer is generally an aqueous solution containing a fixer and others, and the pH is usually 3.8 to 5.8. As a fixing agent, sodium thiosulfate, potassium thiosulfate,
Use of thiosulfates such as ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, as well as organic sulfur compounds capable of forming soluble stable silver complex salts, which are known as fixing agents. You can

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution.

If desired, the fixer may include a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent capable of softening water. And the like.

The developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid having a high viscosity in a semi-kneaded state. Further, it may be diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C.

The black and white silver halide photographic light-sensitive material according to the present invention is preferably processed using an automatic processor.
At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The development replenishment amount is 200 ml or less per 1 m ² in order to reduce the amount of waste liquid. It is preferably 75 ml or more and 180 ml or less per 1 m ² . Particularly preferably, it is 75 ml or more and 160 ml or less per 1 m ² . 75 ml per 1 m ²
If the replenishment amount of the developing solution is less than the above, satisfactory photographic performance cannot be obtained due to desensitization, softening, and the like.

In the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when the processing is performed by using the automatic developing machine is demanded from the desire of shortening the developing time. It is preferably 20 to 60 seconds. The total processing time referred to here includes all process times required for processing a black and white silver halide photographic light-sensitive material, and specifically includes, for example, development, fixing, bleaching, washing with water, stabilization processing and drying necessary for processing. The time including all process times, that is, Dr
It's y to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 20 to 48 seconds.

[0182]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (Preparation of Silver Halide Emulsion A) A silver chloroiodobromide emulsion consisting of 90 mol% silver chloride, 0.2 mol% silver iodide and the rest silver bromide was prepared by the simultaneous mixing method. . At the time of simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ^-8 mol per mol of silver. The resulting emulsion was a cubic, monodisperse grain with a mean grain size of 0.20 μm (variation coefficient 9
%) Emulsion. Then, the emulsion was desalted with a modified gelatin described in JP-A-2-280139 (wherein the amino group in gelatin was replaced with henylcarbamyl, for example, G-8 in JP-A-2-280139). The EAg after desalting was 190 mv at 50 ° C.

The obtained emulsion was adjusted to pH 5.4 and EAg 120 mv, and then the temperature was adjusted to 60 ° C., and chloroauric acid was added to 2.
After adding 2 × 10 ^-5 mol and stirring for 2 minutes, 2.9 × 10 ^-6 mol of inorganic sulfur was added per 1 mol of silver, and chemical ripening was further performed for 30 minutes. At the end of ripening, the following was added per mol of silver.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ⁻³ mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ⁻⁴ mol and gelatin were added. To prepare an emulsion liquid.

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm and subjected to the antistatic treatment described in Example 1 of JP-A-3-92175, the following formulation The silver halide emulsion of No. 1 was coated so that the silver amount was 2.9 g / m ² and the gelatin amount was 1.7 g / m ² .

Furthermore, the following formulation 2 was used as a protective layer on the upper layer.
Was coated so that the amount of gelatin would be 1 g / m ² .
On the opposite undercoat layer, a backing layer of the following formulation 3 was applied so that the amount of gelatin was 2.0 g / m ^2, and a protective layer of the following formulation 4 was applied on the upper layer of the backing layer, the amount of gelatin being 1 g / m ² Was applied so that 9 kinds of samples shown in Table 1 were prepared. Formulation 1 (Silver halide emulsion layer composition) Silver halide emulsion Silver amount 2.9 g / m ² amount Gelatin 1.7 g / m ² amount

[0188]

[Chemical 44]

S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.64 mg / m ² 2-mercapto-6-hydroxypurine 1.7 g / m ² EDTA 50 mg / m ² Formulation 2 (emulsion protective layer composition) ) Gelatin 1.0g / m ² S-1 12mg / m ² Matting agent: Monodisperse silica 22mg / m ² 1,3-vinylsulfonyl-2-propanol 40mg / m ^{2 with an} average particle size of 3.5μm

[0190]

[Chemical formula 45]

[0191] shown in exemplary compounds in Table 1 according to the formulation 3 (the backing layer composition) Gelatin 2.0 g / m ² Saponin ^{133mg / m 2 S-1 6mg} / m 2 Colloidal silica 100 mg / m ² the invention

[0192]

[Chemical formula 46]

Formulation 4 (Backing protective layer composition) Gelatin 1.0 g / m ² matting agent: Monodispersed polymethylmethacrylate 50 mg / m ^{2 having an} average particle size of 5.0 μm / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ^{2 The} temperature of the obtained sample was
It was left in an environment of 50 ° C. and RH of 50% for 3 days for forced deterioration. The obtained sample is adhered to the step wedge and He-Ne
An automatic developing machine for rapid processing (GR-26SR Konica Corp.) using the developer and fixer of the following composition after performing exposure for 10 ^-5 seconds with an interference filter with a wavelength of 633 nm as a substitute for laser light. Was processed under the following conditions.

(Developer Solution Formulation) Sodium sulfite 55 g / liter Potassium carbonate 40 g / liter Hydroquinone 24 g / liter 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (dimesone S) 0.9 g / liter Potassium bromide 5 g / Liter 5-methyl-benzotriazole 0.13 g / liter Boric acid 2.2 g / liter Diethylene glycol 40 g / liter Compound P-1 60 mg / liter

[0195]

[Chemical 47]

Water and potassium hydroxide were added to 1 liter /
Set to pH 10.4.

(Fixing liquid formulation) (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 21 g When using the fixer, the above composition is added to 500 ml of water. A and composition B were melted in this order and finished to 1 liter for use. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development 38 ° C 12 seconds Fixing 35 ° C 10 seconds Washing with water 10 seconds normal temperature 10 seconds Drying 50 ° C 13 seconds Total 45 seconds Each step time is so-called wading conveyance to the next step Including time.

A replenisher having the same composition as that of the developing solution and the fixing solution was used, and 300 m ² of the sample was processed while replenishing the developing solution at a rate of 150 ml / m ² and the fixing solution at 190 ml / m ² . The photographic performance and black spots after processing were examined.

(Measurement Method of Sensitivity / Gamma) The obtained developed sample was measured with PDA-65 (Konica Digital Densitometer).
The sensitivities in the table are relative sensitivities when the sensitivity of Sample No. 1 at a concentration of 3.0 is 100. Further, gamma as an index showing softening is expressed by a tangent of densities of 0.1 and 3.0. In the table, a gamma value of less than 6 cannot be used as a light-sensitive material, and a value of 6 or more but less than 10 still has insufficient hardness. . Gamma value is 10
The above shows for the first time that a super-high contrast image is obtained, and the photosensitive material is sufficiently practical.

(Measurement Method of Fog) The unexposed portion of the obtained developed sample was subjected to density measurement with PDA-65. Values exceeding 0.08 are not practically preferable.

(Measurement method of black spots) The black spots in the unexposed area were evaluated using a magnifying glass of 40 times. The highest rank 5 was one in which no black spots were generated, and the rank was lowered to 4, 3, 2, 1 according to the degree of occurrence of black spots. Ranks 1 and 2 are practically unfavorable levels.

The results are shown in Table 1.

[0204]

[Table 1]

From the results shown in Table 1, it is understood that the samples of the present invention have high sensitivity and gamma, and the generation of black spots is suppressed.

Example 2 Example 2 was conducted in the same manner as in Example 1 except that the nucleation accelerator was Na-7 and the hydrazine derivative according to the present invention and the compound represented by the general formula [1] were used in the backing layer.

The results are shown in Table 2.

[0208]

[Table 2]

From the results shown in Table 2, the sample of the present invention is the same as that of Example 1.
Similarly, it can be seen that the sensitivity and gamma are high and the evaluation of black spots is good.

Example 3 Example except that H-43 was used as the hydrazine derivative and at least one compound selected from the general formulas [2], [3] and [4] according to the present invention was used in the backing layer. Same as 1.

The results are shown in Table 3.

[0212]

[Table 3]

From the results shown in Table 3, it is understood that the samples of the present invention have low fog and good evaluation of black spots.

Example 4 Example 2 was repeated except that the hydrazine derivative was H-33, the nucleation accelerator was Na-5, and the polyhydroxybenzene compound of the present invention was added to the backing layer. The results are shown in Table 4.

[0215]

[Table 4]

From the results shown in Table 4, it can be seen that the samples of the present invention have high sensitivity and gamma.

Example 5 Example 3 was repeated except that the hydrazine derivative was H-33 and the nucleation accelerator was Na-5 to give the redox compound of the present invention in the backing layer.

The results are shown in Table 5.

[0219]

[Table 5]

From the results shown in Table 5, it can be seen that the samples of the present invention have low fog and good evaluation of black spots.

Example 6 By using H-12 as a hydrazine derivative and Na-7 as a nucleation accelerator, at least one compound selected from the water-soluble chlorides, bromides and iodides according to the present invention was prepared in the backing layer. The same procedure was performed as in Example 3 except for the above. The results are shown in Table 6.

[0222]

[Table 6]

From the results shown in Table 6, it can be seen that the samples of the present invention have a low fog and a good evaluation of black spots.

Example 7 The procedure of Example 3 was repeated, except that the hydrazine derivative was H-26 and the nucleation accelerator was Na-17 to give the compound of the general formula [1] according to the present invention in the backing layer.

The results are shown in Table 7.

[0226]

[Table 7]

From the results shown in Table 7, it can be seen that the samples of the present invention have low fog and good evaluation of black spots.

[0228]

EFFECT OF THE INVENTION According to the present invention, a light-sensitive material which has a high contrast even if the pH of the developer is less than 11.0. Sensitivity fluctuations and softening hardly occur even when continuous processing is performed while replenishing the developer with an automatic developing machine, and fog is caused. It was possible to provide a silver halide photographic light-sensitive material having less black spots and an image forming method thereof.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 1/43 5/29 501 5/31

Claims (14)

[Claims] 1. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or an adjacent layer thereof, and at least one layer is provided on the opposite side of the silver halide emulsion layer with a support interposed therebetween. In the silver halide photographic light-sensitive material having the hydrophilic colloid layer, at least one nucleation accelerator is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. Silver halide photographic light-sensitive material. 2. A hydrazine derivative in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. After exposure of the silver halide photographic light-sensitive material having the hydrophilic colloid layer, the developing replenishment amount is 200 per 1 m ² of the light-sensitive material in an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is performed while replenishing at a ratio of not more than ml, at least one nucleation accelerator is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer.
An image forming method characterized by containing a seed. 3. A hydrazine derivative in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. In a silver halide photographic light-sensitive material having a hydrophilic colloid layer as described above, at least one hydrazine derivative is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. Silver photographic light-sensitive material. 4. A hydrazine derivative is contained in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer is provided on the opposite side of the silver halide emulsion layer with the support interposed therebetween. After exposure of the silver halide photographic light-sensitive material having the hydrophilic colloid layer, the developing replenishment amount is 200 per 1 m ² of the light-sensitive material in an automatic processor containing a developer having a pH of less than 11.0.
An image forming method in which development is performed while replenishing at a ratio of not more than ml, wherein at least one hydrazine derivative is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. Forming method. 5. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one layer is provided on the opposite side of the silver halide emulsion layer with the support interposed therebetween. In a silver halide photographic light-sensitive material having a hydrophilic colloid layer of at least one compound represented by the following general formula [1] in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. A silver halide photographic light-sensitive material characterized by containing. [Chemical 1] [In the formula, X and Y represent a nitrogen atom or = C (R ₁₂ )-, and at least one of X and Y is a nitrogen atom. R ₁₁ represents a hydrogen atom, a lower alkyl group, a halogen atom or a nitro group. R ₁₂ represents a hydrogen atom, a lower alkyl group, a halogen atom or a mercapto group. ] 6. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or an adjacent layer thereof, and at least one layer is provided on the opposite side of the silver halide emulsion layer with the support interposed therebetween. After exposure of the silver halide photographic light-sensitive material having the hydrophilic colloid layer, the developing replenishment amount is 200 per 1 m ² of the light-sensitive material in an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is carried out while replenishing at a ratio of not more than ml, in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer, the above-mentioned general formula [1]
An image forming method comprising at least one compound represented by: 7. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or its adjacent layer, and at least one layer is provided on the opposite side of the silver halide emulsion layer with the support interposed therebetween. Of the following formulas [2], [3] and [4] in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. At least one chosen
A silver halide photographic light-sensitive material, characterized by containing various compounds. [Chemical 2] [In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₃₃ , R _41, and R ₄₂ are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, or an alkoxy group. A group, an alkoxycarbonyl group, a substituted or unsubstituted amino group,
It represents an aryl group, a hydroxy group, a mercapto group, a carboxyl group or a salt thereof, or a halogen atom. R ₃₄
And R ₄₃ represents a phosphoric acid group or an optionally substituted alkyl group having 1 to 8 carbon atoms. ] 8. A hydrazine derivative in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. After exposure of the silver halide photographic light-sensitive material having the hydrophilic colloid layer, the developing replenishment rate is 20 per 1 m ² of the light-sensitive material with an automatic processor containing a developer having a pH of less than 11.0.
In the image forming method in which development is performed while replenishing at a ratio of 0 ml or less, in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer, the above-mentioned general formula [2],
An image forming method comprising at least one compound selected from [3] and [4] (Chemical Formula 2). 9. A hydrazine derivative is contained in at least one silver halide emulsion layer on a support and / or an adjacent layer thereof, and at least one layer is provided on the opposite side of the silver halide emulsion layer with the support interposed therebetween. A silver halide photographic light-sensitive material having a hydrophilic colloid layer, wherein at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer contains a polyhydroxybenzene compound. Photographic material. 10. A hydrazine derivative in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. After exposure of the silver halide photographic light-sensitive material having the hydrophilic colloid layer, the developing replenishment amount is set to ² per 1 m ² of the light-sensitive material by an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is carried out while replenishing at a ratio of not more than 00 ml, an image forming method wherein a polyhydroxybenzene compound is contained in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. Method. 11. A hydrazine derivative in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. In a silver halide photographic light-sensitive material having a hydrophilic colloid layer, a redox compound capable of releasing a development inhibitor by being oxidized in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. A silver halide photographic light-sensitive material containing at least one kind. 12. A hydrazine derivative in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. After exposure of the silver halide photographic light-sensitive material having the hydrophilic colloid layer, the developing replenishment amount is set to ² per 1 m ² of the light-sensitive material by an automatic processor containing a developer having a pH of less than 11.0.
A redox compound capable of releasing a development inhibitor by being oxidized in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer in an image forming method in which development is performed while replenishing at a ratio of not more than 00 ml. At least 1
An image forming method characterized by containing a seed. 13. A hydrazine derivative in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. In a silver halide photographic light-sensitive material having a hydrophilic colloid layer of at least one selected from water-soluble chlorides, bromides and iodides in at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. A silver halide photographic light-sensitive material, characterized by containing various compounds. 14. A hydrazine derivative in at least one silver halide emulsion layer and / or its adjacent layer on a support, and at least one layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. After exposure of the silver halide photographic light-sensitive material having the hydrophilic colloid layer, the developing replenishment amount is set to ² per 1 m ² of the light-sensitive material by an automatic processor containing a developer having a pH of less than 11.0.
In an image forming method in which development is carried out while replenishing at a ratio of not more than 00 ml, at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer is selected from water-soluble chloride, bromide and iodide. An image forming method comprising one compound.