JP2896698B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photographic material having a silver halide photosensitive layer on a support, and more particularly to a silver halide photographic material capable of obtaining high contrast.

[Background of the Invention]

The photoengraving step includes a step of converting a continuous tone original into a halftone image. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image having a super-high contrast.

The lithographic silver halide photographic light-sensitive material used in infectious development has, for example, an average particle diameter of 0.2 μm, a narrow particle distribution, uniform particle shape, and a high silver chloride content (at least 50 mol% or more). It consists of a silver chlorobromide emulsion. By processing this lithographic silver halide photographic material with an alkaline hydroquinone developer having a low sulfite ion concentration, an image with high contrast, high sharpness and high resolution can be obtained.

However, since these squirrel-type developers are susceptible to air oxidation, they have extremely poor preservation properties, and it is difficult to maintain a constant development quality even during continuous use.

There has been known a method for quickly obtaining a high-contrast image without using the lith-type developer. For example, U.S. Pat.Nos. 2,419,975, JP-A-51-16623 and 51-20921
As described in JP-A-56-106244 and the like, a hydrazine derivative is contained in a silver halide photosensitive material.

According to these methods, the sulfite ion concentration in the developer can be kept high, and the processing can be performed in a state where the preservation property is enhanced.

However, in these methods, the hydrazine derivative must be treated with a developer having a pH of 11 or more in order to sufficiently exhibit the high contrast. pH 11 or higher
A developer having a pH is more stable than a squirrel developer in which a developing agent is liable to be oxidized when exposed to air, but sometimes an ultra-high contrast image may not be obtained due to oxidation of the developing agent.

To compensate for this drawback, JP-A-63-29751 and EP-A-333,435 and EP-A-345,025 disclose silver halide photographic light-sensitive materials containing a high-contrast agent which makes high-contrast even in a developer having a relatively low pH. ing.

However, when a silver halide photographic light-sensitive material containing such a high contrast agent is processed with a developer having a pH of less than 11, the high contrast is insufficient and satisfactory dot performance cannot be obtained at present. .

On the other hand, European Patent 364166 and JP-A-62-22241
No. 60-140340, No. 62-250439, No. 62-280733, etc., describe a nucleation accelerator for accelerating high contrast, and indeed these compounds are added to the emulsion layer. As a result, it has been found that the dot performance is improved, but there is a problem that sand-like or pin-like fog, that is, a so-called black pin is generated in the dot and impairs the quality of the dot image.

Therefore, a photographic material using an effective high contrast agent and a nucleation accelerator which has solved the above-mentioned problems has been desired.

[Object of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material that has high photographic characteristics even when processed with a developer having a pH of less than 11, and has good halftone performance by suppressing fog generated in halftone images. To provide.

[Configuration of the invention]

The above object of the present invention has been attained by a silver halide photographic material having the following constitution.

That is, in a silver halide photographic material having at least one silver halide emulsion layer, the following general formula [A]
Containing at least one hydrazine compound represented by
The above object has been attained by a silver halide photographic material characterized by containing at least one nucleation promoting compound selected from an amine compound, a hydrazine compound and a quaternary onium salt compound.

In the formula, Ar represents an aryl group, and X is -NR ₁ R ₂ or -OR ₃
Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic ring. R ₁ and R ₂ may represent an oxy group and may form a ring together with the nitrogen atom.

R ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

R represents a hydrogen atom or an alkyl group, n represents 0 or 1, and m represents an integer of 1 to 3.

However, in the compound represented by the general formula [A], at least one R has an adsorption promoting group to silver halide,
Alternatively, diffusion resistance is given as the sum of R in the molecule.

The compound represented by the general formula [A] includes -NHNH-
Wherein at least any one of H is substituted with a substituent.

The general formula [A] will be described in more detail.
Represents an aryl group (eg, phenyl, naphthyl, etc.).

R ₁ and R ₂ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, 4- (2,4-di-t-amylphenoxy) butyl, benzyl, trifluoroethyl, etc.) An alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl, etc.), an alkynyl group (eg, propargyl, butynyl, pentynyl, etc.), an aryl group (eg, phenyl,
Naphthyl, cyanophenyl, methoxyphenyl, etc.), a heterocyclic group (for example, pyridine, thiophene, an unsaturated heterocyclic group such as furan or tetrahydrofuran, sulfolane,
A saturated heterocyclic group such as 2,2,6,6-tetramethylpiperidine), a hydroxyl group, an alkoxy group (e.g., methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.),
Represents an alkenyloxy group (eg, allyloxy, butenyloxy, etc.), an alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), an aryloxy group (eg, phenoxy, naphthyloxy, etc.) or a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.), R ₁ and R ₂ may form a ring together with the nitrogen atom (eg, piperidine, piperazine, morpholine, etc.).

An alkyl group represented by R ₃ , an alkenyl group, an alkynyl group,
As the aryl group and the heterocyclic group, specifically, the above-described R ₁
And include the same groups as those mentioned R _2.

Examples of the alkyl group represented by R include groups such as methyl, ethyl, propyl, butyl, and benzyl.

Various substituents can be introduced into the alkyl group represented by R. Examples of such groups include a carbamoyl group, a ureidocarbonyl group, an oxycarbonyl group, an acylamino group, a sulfonamide group, a carbonyloxy group, and a sulfamoyl group. No.

A diffusion-resistant group or a silver halide adsorption promoting group can be introduced through these substituents.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable.

The ballast group is a group having a carbon number of 8 or more which is relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like. be able to.

When a plurality of R- (O) n- groups are present in a molecule, any substance may be used as long as it imparts diffusion resistance (as a whole) to the total of R groups.

Silver halide adsorption promoting groups include thiourea groups, thiourethane groups, heterocyclic thioamide groups, mercapto heterocyclic groups,
Examples include groups described in US Pat. No. 4,385,108, such as a triazole group.

Various substituents can be introduced into the aryl group represented by Ar. Examples of the substituent that can be introduced include, for example, a halogen atom and alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfamoyl, acyl, amino, alkylamino, arylamino, acylamino ,
Examples include groups such as sulfonamide, arylaminothiocarbonylamino, hydroxyl, carboxyl, sulfo, nitro, cyano and the like.

In the general formula [A], H of —NHNH—, that is, the hydrogen atom of hydrazine is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl,
It may be substituted with a substituent such as trifluoroacetyl, ethoxycarbonyl and the like, and an oxalyl group (for example, ethoxyzalyl, pyruvoyl and the like), and the compound represented by the general formula [A] includes such a compound.

In the present invention, a more preferred compound is that at least one of R ₁ and R _{2 in} the general formula (A) represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group or an alkoxy group, or R ₃ represents an alkynyl group. Or a compound representing a saturated heterocyclic group.

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

The compound represented by the general formula [A] according to the present invention is described in British Patent No. 2,011,391, U.S. Patent No. 4,686,167, European Patent No. 301,799, JP-A-62-180361, and JP-A-62-178246.
And can be easily synthesized according to the synthesis method described in No.

For example, the exemplary compound (1) can be synthesized by the following method.

Compound (13) can be synthesized by the following method.

Other compounds can be similarly synthesized.

In the present invention, the amine compound, the hydrazine compound, and the quaternary onium salt compound of the nucleation promoting compound used in combination with the compound represented by the general formula (A) include compounds of the following general formulas (I) to (VI). No. Among these, preferred compounds include [V] -I, [V] -II, [V] -II
And compounds of I, [VI] -I, [VI] -II and [VI] -III.

R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent. R ₁ , R ₂ and R ₃ may be linked to each other to form a ring.

Examples of the substituent represented by R ₁ , R ₂ , and R ₃ include an alkyl group (for example, a group such as methyl, ethyl, propyl, butyl, hexyl, and cyclohexyl), an alkenyl group (for example, a group such as allyl and butenyl), and an alkynyl group. (Eg, groups such as propargyl and butynyl), aryl groups (eg, groups such as phenyl and naphthyl), and heterocyclic groups (eg, piperidinyl, piperazinyl, morpholinyl, pyridyl, furyl,
Thienyl, tetrahydrofuryl, tetrahydrothienyl, sulfolanyl, etc.).

Examples of the ring which may be formed by connecting R ₁ , R ₂ and R ₃ to each other include rings such as piperidine, morpholine, piperazine, quinuclidine and pyridine.

The groups represented by R ₁ , R ₂ , and R ₃ may be further substituted with substituents (for example, groups such as hydroxyl, alkoxy, aryloxy, carboxyl, sulfo, alkyl, and aryl). R ₁ , R ₂ and R ₃ are preferably a hydrogen atom and an alkyl group.

 A typical example is shown below.

 Q represents an N or P atom;₁, R_Two, R_Three, R_FourAre each water
Represents an element atom or a substitutable group. X Represents an anion
You. R₁, R_Two, R_Three, R_FourMay be linked to each other to form a ring
No.

Examples of the substitutable group represented by R ₁ , R ₂ , R ₃ , and R ₄ include groups such as alkyl, alkenyl, alkynyl, aryl, heterocycle, and amino. I], R ₁ , R ₂ , and R ₃ .

Examples of the ring that can be formed by R ₁ , R ₂ , R ₃ , and R ₄ include the same rings as those described as the ring that can be formed by R ₁ , R ₂ , and R ₃ in formula [I].

 X Examples of the anion represented by a halide ion,
Sulfate ion, nitrate ion, acetate ion, paratoluene
Inorganic and organic anions such as sulfonic acid ions;
You.

 A typical example is shown below.

R ₁ and R ₂ represent an alkyl group, and R ₁ and R ₂ may combine to form a ring. R ₃ represents an alkyl group, an aryl group, or a heterocyclic group, and A represents an alkylene group.

Y is _{-CONR 4 -, - OCONR 4 -} , - NR 4 CONR 4 -, - NR 4 CO
O -, - COO -, - OCO -, - CO -, - OCOO -, - NR 4 CO
−, −SO ₂ NR ₄ −, −NR ₄ SO ₂ −, −NR ₄ SO ₂ NR ₄ −, −SO
_{2 -, - S -, -} 0 -, - NR 4 -, - N = represents a group, R ₄ represents a hydrogen atom or an alkyl group.

The alkyl groups represented by R ₁ and R ₂ include those represented by the general formula [I]
Examples are the same as the alkyl groups of R ₁ , R ₂ and R ₃ described above, and the same ring is also formed by R ₁ and R ₂ .

Alkyl group represented by R _3, aryl group, alkyl group represented by R _1, R _2, R ₃ also general heterocyclic groups (I), an aryl group include those similar to the heterocyclic group.

Examples of the alkylene group represented by A include methylene, ethylene, trimethylene, and tetramethylene, and examples of the substituent of A include an aryl group, an alkoxy group,
Examples thereof include a hydroxyl group and a halogen atom.

The alkyl group represented by R ₄ is preferably a lower alkyl group having 1 to 5 carbon atoms or an aralkyl group (such as a benzyl group).

 The following representative specific examples are shown.

R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R ₁ , R ₂ and E may form a ring.

E Ri is at least one group containing a group represented by CH ₂ CH ₂ O _{n, n} is an integer of 2 or more.

R _1, the alkyl group represented by R _2, an alkenyl group, an alkynyl group, an aryl group, the ring may form a heterocyclic group and R _1, R _2, E, R _1, R of formula (I) ₂ include the same as described in R _3.

 A typical example is shown below.

R ₁ , R ₂ , and R ₃ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

However, at least one of R ₁ , R ₂ and R ₃ represents an alkenyl group or an alkynyl group, or at least one of R ₁ and R ₂ represents an aryl group or a heterocyclic group. R ₁ , R ₂ , L and R ₃ may form a ring. L represents a linking group.

The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₁ , R ₂ and R ₃ are the same as the groups exemplified for R ₁ , R ₂ and R ₃ in the general formula [I]. Is mentioned.

Examples of the ring that can be formed by R ₁ , R ₂ , L, and R ₃ include a hetero ring such as piperidine, morpholine, and pyrrolidine.

As the linking group represented by L, for example, the general formula [III]
And -AY-.

 A typical example is shown below.

R ₁ , R ₂ , and R ₄ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R ₃ represents a hydrogen atom or a substitutable group.

L represents a linking group, and n represents an integer of 0 or 1. R ₁ ,
R ₂ , R ₃ , L and R ₄ may be linked to form a ring.

The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₁ , R ₂ and R ₄ are the same as those described for R ₁ , R ₂ and R ₃ in the general formula [I]. The group of is mentioned.

Examples of the substitutable group represented by R ₃ include alkyl, alkenyl, aryl, and heterocyclic groups,
The same groups as described above can be mentioned.

L represents a linking group, for example, -CO-, -COO-, -CON
R ₅ —, —SO ₂ —, —SO ₂ NR ₅ — and the like. R ₅ represents a hydrogen atom or a substitutable group.

Examples of the ring that can be formed by R ₁ , R ₂ , R ₃ , L, and R ₄ include a hetero ring such as piperidine and morpholine.

 A typical example is shown below.

R ₁ represents a hydrogen atom or a substituent, and R ₂ represents an alkyl, alkenyl, alkynyl, aryl, or heterocyclic group. L represents a linking group.

Represents a nitrogen-containing heterocyclic ring. n represents an integer of 0 or 1.
R ₁ And may form a ring together.

Examples of the alkyl, alkenyl, alkynyl, aryl, and heterocyclic groups represented by R ₂ include R ₁ ,
The same groups as those described for R ₂ and R ₃ can be mentioned. Examples of the substituent among the groups represented by R ₁ include the same groups as those described for R ₂ above.

And a heterocycle represented by R ₁ Examples of the hetero ring that can be formed with, for example, quinuclidine,
Heterocycles such as piperidine and pyrazolidine are exemplified.

As the linking group represented by L, for example, the general formula [III]
And the same as those represented by Y.

 A typical example is shown below.

R ₁ and R ₂ are an alkyl group, an alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group, and R ₃ represents a hydrogen atom or a substituent.

R ₄ Is a group containing at least one group represented by R represents a hydrogen atom or an alkyl group; X represents an O, S or NH group;
Y represents a hydrogen atom or an OH group, and n represents an integer of 2 or more. R ₁ , R ₂ , R ₃ and R ₄ may be linked to form a ring.

The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₁ and R ₂ are the same as those described for R ₁ , R ₂ and R _{3 in} the general formula [I]. The same is mentioned.

Examples of the substituent among the groups represented by R ₃ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, an oxycarbonyl group, and a carbamoyl group. Among the substituents represented by R _3, an alkyl group, an alkenyl group, an alkynyl group,
As the aryl group and the heterocyclic group, R ₁ ,
The same groups as described for R ₂ and R ₃ can be mentioned.

Examples of the acyl group include acetyl and benzoyl.Examples of the sulfonyl group include methanesulfonyl and toluenesulfonyl.Examples of the oxycarbonyl group include ethoxycarbonyl and phenoxycarbonyl.Examples of the carbamoyl group include methyl. Carbamoyl, phenylcarbamoyl and the like.

The ring which can be formed by R ₁ , R ₂ , R ₃ and R ₄ includes pyridine,
And a ring such as morpholinone.

The alkyl group among the groups represented by R is methyl, ethyl and the like, and a methyl group is preferable.

 A typical example is shown below.

R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R ₁ , R ₂ and T may form a ring.

T is Is a group containing at least one group represented by

R represents a hydrogen atom or an alkyl group; X represents O, S or NH
Y represents a hydrogen atom or an OH group, and n represents an integer of 2 or more. However, when R is a hydrogen atom, X represents an S or NH group.

Among the groups represented by R ₁ and R ₂ , alkyl, alkenyl, alkynyl, aryl, and heterocyclic groups include
The same groups as those described for R ₁ , R ₂ and R ₃ in the general formula [I] can be mentioned.

Examples of the ring that can be formed by R ₁ , R ₂ , and T include a hetero ring such as piperidine, morpholine, quinuclidine, and pyrazolidine.

Examples of the alkyl group represented by R include methyl and ethyl, and a methyl group is preferable.

 A typical example is shown below.

R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R ₁ , R ₂ and G may form a ring.

G contains at least one group represented by CH ₂ CH ₂ O _n, and either hydrophobic substituent constant π value comprises at least two substituents of -0.5 to 1.0, or π value than -1.0 It shall contain at least one small substituent. n represents an integer of 2 or more.

Of the groups represented by R ₁ and R ₂ , alkyl, alkenyl,
Examples of the alkynyl, aryl and heterocyclic groups include the same groups as those described for R ₁ , R ₂ and R ₃ in the general formula [I].

Examples of the ring that can be formed by R ₁ , R ₂ , and G include rings such as piperidine, quinuclidine, and morpholine.

The hydrophobic substituent constant π is described in the structure-activity relationship of drugs (Nankodo), pp. 79-103 (Showa 54).

 As a substituent having a π value of -0.5 to -1.0, for example, -CN,
−OH, −OS_TwoCH_Three, −OCOCH_Three,−NHCOCH_Three,As a substituent having a π value smaller than -1.0.
Is, for example, -CONH_Two, −CONHOH, −CONHCH_Three, -NH_Two, -NH
CONH_Two, −NHCSNH_Two, -NHSO_TwoCH_Three, -N (CH_Three)_Three, −
O , −OCONH_Two, −SO_Three , −SO_TwoNH_Two, −SOCH_Three, −SO_TwoC
H_Three, −COO And the like.

 A typical example is shown below.

In the silver halide photographic light-sensitive material capable of obtaining a high-contrast image to which the present invention is applied, at least one hydrazine compound represented by the general formula [A] and one represented by the formulas [I] to [VI] are used. The nucleation promoting compound is contained in the photographic material. The amount of the compounds represented by the general formulas [A] and [I] to [VI] contained in the photographic material is contained in the photographic material. 5 × 10 ^-7 per mole of silver halide
It is preferably from 5 mol to 5 × 10 ^-1 mol.

In particular, it is preferably in the range of 5 × 10 ^-6 mol to 1 × 10 ^-2 mol.

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one layer may be provided on both sides of the support. The silver halide emulsion can be coated directly on the support or can be coated via another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer may be provided as a protective layer on the emulsion layer. Further, the silver halide emulsion layers may be separately applied to silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between the silver halide emulsion layers. That is, an intermediate layer made of a hydrophilic colloid may be provided as necessary. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, and a backing layer may be provided between the silver halide emulsion layer and the protective layer.

The compounds represented by the general formulas [A] and [I] to [VI] are used in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention. To be included.

Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described. As silver halide, 4
It is silver iodobromide or silver iodobromide containing not more than 3 mol% of silver iodide, preferably not more than 3 mol%. The average grain size of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, and more preferably 0.10 to 0.40 μm.

The particle size distribution of the silver halide grains used in the present invention is arbitrary, but is preferably adjusted so that the value of the monodispersity defined below is from 1 to 20%, more preferably from 5 to 15%. I do.

Here, the monodispersity is defined as a numerical value (%) obtained by multiplying a value (coefficient of variation) obtained by dividing the standard deviation of the particle diameter by the average particle diameter by 100. For the sake of convenience, the grain size of silver halide grains is represented by the edge length in the case of cubic grains, and other grains (8
Is calculated by the square root of the projected area.

In practicing the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, silver iodobromide in the core and bromide in the shell. What consists of silver iodobromide grains which are silver can be used. At this time, iodine can be contained in any layer within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention may be formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium during grain formation and / or growth. Metal ions can be added using at least one selected from salts (including complex salts) and iron salts (including complex salts), and these metal elements can be contained inside the particles and / or on the surface of the particles. By placing in a suitable reducing atmosphere, a reduction sensitizing nucleus can be provided inside the grain and / or on the grain surface.

Furthermore, silver halide can be sensitized by various chemical sensitizers. As the sensitizer, for example, active gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiacinate, etc.), selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.) ), Reduction sensitizer (triethylenetetramine, silver chloride 1)
Tin etc.), for example, potassium chloroaulite, potassium aurithiocyanate, potassium chloroaurate, 2-
Various noble metal sensitizers represented by aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite and the like can be used alone or in combination of two or more. When a gold sensitizer is used, rhodamonmon can be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains having a surface sensitivity higher than the internal sensitivity, that is, silver halide grains giving a so-called negative image. Can be enhanced.

The silver halide emulsion used in the present invention may be a mercapto (1-phenyl-5-mercaptotetrazole,
Stabilization or fog suppression can be performed using 2-mercaptobenzthiazole), benzotriazoles (5-bromobenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole), and the like.

In the photosensitive silver halide emulsion layer or its adjacent layer, Research Disclosure 1746 is used for the purpose of increasing sensitivity, increasing contrast, or accelerating development.
Compounds described in No. 3 in the paragraphs XXI BD can be added.

Further, it is preferable to add a compound represented by the following general formula [P].

Formula (P) _{R 1 -OCH 2 CH 2 O n} H [wherein R ₁ represents an aromatic ring having a hydrogen atom or unsubstituted or substituted groups,, n represents an integer of 10-200. First, specific examples which are more preferable than the compound represented by the general formula [P] will be given. Although the molecular weight is preferably 1500 or more,
It is not limited to these.

These compounds are commercially available and can be easily obtained. These compounds are preferably added in an amount of 0.01 to 4.0 mol per mol of silver halide, more preferably 0.02 to 2 mol. Also, it is preferable to include it in the emulsion layer. Further, two or more compounds having different values of n may be included.

The silver halide emulsion used in the present invention may contain a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener, and the like. General formulas [A] and [I] according to the present invention
When adding the compound of ~ ~ (VI) to the hydrophilic colloid layer,
Gelatin is preferred as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably applied on both sides of the support at 10 g / m ² or less.

Examples of the support that can be used in the practice of the present invention include polyester films such as baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyethylene terephthalate. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

For the development processing of the silver halide photographic light-sensitive material of the present invention, for example, the following developing agents are used.

Representative HO- (CH = CH) n-OH type developing agents include hydroquinone, and catechol, pyrogallol and the like.

As the HO- (CH = CH) n-NH ₂ type developer, ortho- and para-aminophenols or aminopyrazolone are typical, and N-methyl-p-aminophenol,
N-β-hydroxyethyl-p-aminophenol, p
-Hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

Heterocyclic developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl -4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
And pyrazolidones.

In addition, The James of the Theory of the James
Photographic Process 4th Edition (The Theory of th
e Photographic Process, Fourth Edition) 291-344
Pages and Journal of the American Chemical
Society (Journal of the American Chemical Socie
ty) Developers described in Vol. 73, page 3, 100 (1951) can be used effectively in the present invention. These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination.

The effect of the present invention is not impaired even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in a developer used for developing the light-sensitive material of the present invention. Further, a hydroxylamine or hydrazine compound may be used as a preservative. In addition, it can have a pH adjustment and buffer function with caustic alkali, alkali carbonate, amine or the like as used in general black and white developers.

A feature of the present invention is that a developer having a pH of less than 11 can be used. In the developing solution, an inorganic development inhibitor such as promcali, an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine, 1-phenyl-5-mercaptotetrazole, ethylenediamine Metal ion scavengers such as acetic acid, development accelerators such as methanol, ethanol, benzyl alcohol and polyalkylene oxide; surfactants such as sodium alkylaryl sulfonate, natural saponins, saccharides and alkyl esters of the above compounds, glutaraldehyde It is optional to add a hardening agent such as formalin and glyoxal, and an ionic strength adjusting agent such as sodium sulfate.

In the developer used in the present invention, as an organic solvent, alkanolamines such as diethanolamine and triethanolamine, glycols such as diethylene glycol and triethylene glycol, and diethylamino-
Alkylamino alcohols such as 1,2-propanediol and butylaminopropanol may be contained.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by a double jet method. During this mixing, 8 × 10 ^-7 mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion is
Cubic monodisperse particles having an average particle size of 0.20 μm (coefficient of variation 9.5
%). This emulsion contains per mole of silver
After adding 6.5 ml of a 1% potassium iodide aqueous solution, modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added, and the same method as in Example 1 of Japanese Patent Application No. 1-1890787 was added. Washed and desalted. The pAg at 40 ° C. after desalting was 8.0. Further, the following compounds [A], [B],
The mixture of [C] was added.

(Preparation of silver halide photographic material) One undercoat layer of a 100 μm thick polyethylene terephthalate film having a 0.1 μm thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On top, a silver halide emulsion layer having the following formula (1) was prepared with a gelatin amount of 2.0 g / m ² ,
Coating was performed so that the silver amount was 3.2 g / m ^2, and an emulsion protective layer having the following formula (2) was further coated thereon so that the gelatin amount was 1.0 g / m ² . A backing layer of the following formula (3) is provided on the other undercoat layer on the opposite side so that the amount of gelatin is 2.4 g / m ² , and further, a backing protection of the following formula (4) is further provided thereon. The layers were applied so that the amount of gelatin became 1.0 g / m ² , and Sample Nos. 1 to 30 were obtained.

Formulation (4) (composition of backing protective layer) Gelatin 1 g / m ² Matting agent: polymethyl methacrylate 15 mg / m ^{2 with} average particle size of 3.0 to 5.0 μm Surfactant: S-2 10 mg / m ² Hardening agent: glyoxal 25 mg / m ² 〃: H-1 35 mg / m ^{2 The} obtained sample was subjected to a dot quality test by the following method.

(Dot quality test method) A halftone screen (150 lines / inch) with a halftone area of 50% was partially attached to the step wedge, and the sample was brought into close contact with it and exposed for 5 seconds with a xenon light source. The following developing solution and the following fixing solution were charged in the automatic processing machine for rapid processing under the following conditions, and the dot quality of the sample was 100%.
Observation was made with a double magnifier, and a sample with high halftone quality was assigned a rank of "5", and the ranks were sequentially reduced to "4", "3", "2", and "1". Note that the ranks “1” and “2” are levels that are not preferable for practical use.

Fog in a halftone dot was evaluated in the same manner, and a sample having no black pin in the halftone dot was set to the highest rank "5", and a rank "5" was selected according to the degree of occurrence of a black pin in the halftone dot. 4 ",
"3", "2", "1" and their ranks were sequentially reduced and evaluated. In addition, in the ranks "1" and "2", the black pins are too large, which is not a practically preferable level.

Fixer 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 g Sodium citrate dihydrate 2 g (Composition B) Pure water (ion exchange water) 17 ml Sulfuric acid (50% w / v aqueous solution) 4.7 g Aluminum sulfate 26.5 g (aqueous solution with an equivalent content of 8.1 w / v% in terms of Al ₂ O ₃ ) Melted and finished to 1 for use. The pH of the fixing solution was adjusted to 4.8 with acetic acid.

(Processing conditions) (Process) (Temperature) (Time) Current image 40 ° C 15 seconds Fixed 35 ° C 15 seconds Rinse 30 ° C 10 seconds Dry 50 ° C 10 seconds In addition, halogenation in formula (1) The following compounds (a) and (b) were added as comparative compounds of the hydrazine derivative according to the present invention added to the silver emulsion layer.

As is clear from Table 1, the sample according to the present invention has better dot quality and black pin compared to the comparison.

[Effects of the Invention] According to the present invention, a silver halide photographic light-sensitive material having high contrast, low fog and good halftone dot performance even when processed with a low-pH developer having a pH of less than 11 was provided.

Continuation of the front page (56) References JP-A-2-97937 (JP, A) JP-A-1-283548 (JP, A) JP-A-2-947 (JP, A) JP-A-2-41 (JP) , A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 1/06 501 G03C 1/295

Claims (1)

(57) [Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer, comprising at least one hydrazine compound represented by the following general formula [A], and an amine compound, a hydrazine compound: A silver halide photographic light-sensitive material comprising at least one nucleation promoting compound selected from quaternary onium salt compounds. [In the formula, Ar represents an aryl group, and X represents -NR ₁ R ₂ or -OR ₃
The stands, each R ₁ and R ₂ are hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, alkynyloxy group, an aryloxy group or a heterocyclic Represents an oxy group, and R ₁ and R ₂ may form a ring together with a nitrogen atom. R ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R represents a hydrogen atom or an alkyl group, n represents 0 or 1, and m represents an integer of 1 to 3. However, in the compound represented by the general formula [A], at least one R has a group that promotes adsorption to silver halide, or imparts diffusion resistance as the total of R in the molecule. The compound represented by the general formula [A] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent. ]