JPH06258751A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material superior in reproduction fidelity to an original and image quality by incorporating a hydrazine derivative and a specified compound. CONSTITUTION:The silver halide photographic sensitive material contains the hydrazine derivative and the compound represented by formula I in which each of A and B is a nonmetallic atomic group necessary to form a hetero ring; X<-> is an anion, such as Cl<->, Br<->, ClO4<->, or CH3SO3<->, and it is preferred to incorporate the compounds represented by formulae II and III in which each of R1-R3 is H or an alkyl or the like or each may form a ring; Ar is an optionally substituted aryl or heterocyclic group; and R is an optionally substituted alkyl or alkenyl group or the like, and each compound is, especially preferably, an aliphatic tertiary compound and each has, preferably, a diffusion-resistant group or a silver halideadsorptive group in the molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultrahigh-contrast silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material excellent in reproducibility, image quality and development stability.

[0002]

2. Description of the Related Art It is known that a certain type of silver halide can be used to form a photographic image having an extremely high contrast, and such a photographic image forming method is used in the field of photolithography. For example, a lith-type silver halide light-sensitive material made of silver chlorobromide (at least a silver chloride content of 50% or more) is well known to those skilled in the art, but it is theoretically impossible to increase the concentration of sulfurous acid, so that it is not susceptible to air oxidation. On the other hand, it had the drawback of being unstable.

Therefore, the instability of the image forming method by the developing method (lith development system) as described above is eliminated, and the image is developed with a developer having good storage stability to obtain an image having super-high contrast photographic characteristics. A forming system is desired, and U.S. Pat. Nos. 4,166,742, 4,168,977, 4,221,857, and 4,2
24,401, 4,243,739, 4,272,606, 4,311,78
The surface latent image type silver halide photographic light-sensitive material added with a specific hydrazine compound as shown in No. 1 has a pH of 11.0 to 1
In 2.3, a system has been proposed which forms a super-high contrast negative image in which γ exceeds 10 by processing with a developer containing 0.15 mol / l or more of a sulfite preservative and having good storage stability.
However, this new image forming system has a drawback in that it is impossible to faithfully reproduce an image because the hydrazine compound causes a remarkable nucleation effect to the unexposed area around the exposed area and the image is substantially enlarged. It was For example, particularly strict quality is required, such as enlargement (expansion) and reduction (contraction) quality of halftone pictures in the line drawing process, bright reproducibility in bright room returning process, blank character quality or scanner output in color separation process. In the field, there was a problem with image quality.

Further, in this new image forming system, since the pH of the developing solution is high, it is easily affected by air oxidation and the storability of the developing solution is not sufficient. Therefore, a highly active hydrazine compound that gives a high contrast even in a developer having a pH of about 10.5 is a US patent.
167,814, U.S. Patent 4,988,604, U.S. Patent 4,994,346
And JP-A-63-234244 and 63-249838. In such an image forming system, there are great merits such that a carbonate buffer can be used in place of a phosphate buffer which has a great influence on the environment and which is not easily affected by air oxidation and has excellent storability of a developer. However, when these highly active hydrazine compounds are used, the nucleating action is larger than that of hydrazine compounds that sufficiently harden at pH 11 or higher, so that the faithful image reproducibility is further inferior to that of the conventional system. A photosensitive material having image reproducibility has been desired.

[0005]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a light-sensitive material which forms a super-high contrast image by the nucleating action of a hydrazine compound and which is excellent in faithful reproducibility of an original and in image quality. Is provided.

Secondly, it is to provide a light-sensitive material which is excellent in image quality and stability of the developing solution by using a highly active hydrazine compound which causes a high contrast even in a developing solution having a pH of 11 or less.

[0007]

The above object of the present invention is achieved by a silver halide photographic light-sensitive material containing a hydrazine derivative and a compound represented by the general formula [1] (Chemical formula 1). To be done.

In the present invention, the above general formula [4]
It is a preferred embodiment to contain the hydrazine derivative represented by (Chemical formula 4) and the compound represented by the general formula [2] (Chemical formula 2) or [3] (Chemical formula 3).

The present invention will be specifically described below.

As the hydrazine derivative used in the present invention, the compound represented by the above general formula [4] is used.

The general formula [4] 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, and these are further suitable substituents (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group,
Sulfonamide group, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [4] 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 [4] is preferably a monocyclic or condensed ring heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, for example, 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.

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.), aryloxy Carbonyl group (eg phenoxycarbonyl etc.), sulfamoyl group (eg dimethylsulfamoyl etc.), sulfinamoyl group (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 (discussed below with respect to general formula [5]) or a heterocyclic group ( For example, a pyridine ring, a pyridinium ring, etc.) is represented.

B in the general formula [4] represents A ₂ and a nitrogen atom to which they are bonded,

[0019]

[Chemical 6]

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, particularly preferred are the compounds represented by the following general formula [5].

[0025]

[Chemical 7]

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

[0027]

[Chemical 8]

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, Or a heterocyclic oxy group, R ₈ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Alternatively, it represents a heterocyclic group. A ₁ and A ₂ are A in the general formula [4].
₁ and A ₂ each represent the same group.

The general formula [5] will be described in more detail.

The aryl group represented by R ₄ is preferably a monocyclic or 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 an aryl group, and a benzene ring is most preferred.

[0034] A ₁ and A _2, A ₁ and A ₂ in the general formula [4]
And a hydrogen atom are the most preferable.

R ₅ is

[0036]

[Chemical 9]

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, quinuclidinyl, 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 compound represented by the general formula [5] are shown below. However, the present invention is not limited to these.

[0039]

[Chemical 10]

[0040]

[Chemical 11]

[0041]

[Chemical 12]

[0042]

[Chemical 13]

[0043]

[Chemical 14]

[0044]

[Chemical 15]

[0045]

[Chemical 16]

The method of synthesizing the compound represented by the general formula [4] 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 content of the compound represented by the general formula [4] of 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, when the compound represented by the general formula [4] is contained in the photographic light-sensitive material, it is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

Next, the compound represented by the general formula [1] used in the present invention will be explained.

The non-metal atom group A and / or B necessary for forming the heterocycle of the compound is-[C (R ₁ ) H] m- [wherein R ₁ is a hydrogen atom or a lower alkyl group, m Represents 2 or 3. ] What is represented by these is preferable. Representative specific examples of the compound represented by the general formula [1] are shown below.

[0051]

[Chemical 17]

The compound represented by the general formula [1] of the present invention can generally be easily synthesized from an azole compound having a methylmercapto group.

Synthesis Example-1 (Exemplified Compound 1-3) 16 g of 2-methylthiobenzothiazole and 25 g of 1,3-dibromopropane were heated at 160 ° C. for 4 hours. After cooling, the precipitated crystal was filtered and recrystallized from ethanol to obtain 14 g of the target compound as a needle crystal having a melting point of 260 ° C.

Synthesis Example-2 (Exemplified Compound 1-7) Chemical Abstrakuts Volume 72 3
It can be synthesized by the method of page 1666 (1970).

The addition amount of the compound of the general formula [1] used in the present invention is slightly different depending on the kind of binder such as gelatin, the difference of drying condition at the time of production, the difference of silver halide of silver halide emulsion and the like. , About 0.01 to 1 mol of silver
A range of 1000 mg is preferred. 0.1 to 50 mg is particularly desirable,
Usually, it is used by dissolving it in a solvent such as methanol to a concentration of 0.1 to 1%. As for the timing of addition, any step may be added before the coating and drying step in the photographic light-sensitive material manufacturing step.

The compounds represented by the general formula [1] used in the present invention are Japanese Patent Publication Nos. 47-41095, 48-39169 and 49-481.
No. 72 exemplifies a method for hardening a protein, a method for preparing a hardening agent for gelatin, or a method for hardening a vinyl polymer. In these publications, halogen generated by using a hydrazine derivative which is a feature of the present invention is disclosed. No suggestion has been made to suppress deterioration of the quality of photographic images of silver halide photographic light-sensitive materials. Moreover, the present invention does not suppress the deterioration of the image quality caused by the nucleation development of the hydrazine derivative by utilizing the curing action of the binder such as gelatin.

According to the present invention, it is possible to maintain stable photographic performance which cannot be obtained by the method utilizing the hardening action of the binder such as gelatin. This is surprisingly unexpected, but the inventors of the present invention applied the compound represented by the general formula [1] to the silver halide photographic light-sensitive material obtained by the nucleation development of the hydrazine derivative. Very effectively suppresses the deterioration of the image quality of the material, and adversely affects the properties of the silver halide photographic light-sensitive material that may occur when the conventional hardening action of a binder such as gelatin is used (for example, increase in fog, decrease in sensitivity, etc.). It has been found to have advantages without the drawbacks that it exerts.

As the hydrazine derivative, the above-mentioned general formula [4]
In the silver halide emulsion layer, at least one of the nucleation promoting compounds described in JP-A-4-98239, page 607 (7), lower left column, line 1 to page 626 (26), lower left column, line 11 is used. And / or it is preferably contained in the non-light-sensitive layer on the side of the silver halide emulsion layer on the support.

Examples of the nucleation accelerator include those represented by the above general formula [2] (Chemical formula 2) or [3] (Chemical formula 3).

In the general formula [2], R ₁ , R ₂ and R ₃ represent 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 nitrogen-containing heterocycles, mercapto groups, thioether groups, thione groups, thiourea groups and the like.

Specific compounds include those shown below.

[0062]

[Chemical 18]

[0063]

[Chemical 19]

[0064]

[Chemical 20]

In the general formula [3], Ar represents a substituted or unsubstituted aryl group or a 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.

[0067]

[Chemical 21]

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes, for example, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those commonly used in ordinary silver halide emulsions such as silver halide can be used, but silver chlorobromide, silver bromide or silver iodobromide containing 4 mol% or less of silver iodide is preferable. .

The above-mentioned silver halide grains contained in the silver halide emulsion are (standard deviation of grain size) / (average grain size)
Monodisperse particles having a coefficient of variation represented by × 100 of 15% or less are preferable.

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention.

For example, various chemical sensitizers, color toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, UV absorbing agents are used in silver halide photographic emulsions and backing layers. Agents, anti-irradiation dyes, heavy metals, matting agents and the like can be further incorporated by various methods.
Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer.

More specifically, these additives are described in Research Disclosure, Vol. 176, Item / 7643 (December 1978).
And 187, Item / 8716 (November 1979). As the support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass , Metals and the like. These supports are subjected to a surface treatment if necessary.

[0073]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 (Preparation of silver halide photographic emulsion) An aqueous silver nitrate solution and KBr, KI were mixed by a control double jet method so that the silver halide composition was 98 mol% silver bromide and 2 mol% silver iodide. To grow silver halide grains. At this time pAg
7.8, pH 2.0 and mix, K just before the end of particle formation
₂ IrCl ₆ was added in an amount of 6 × 10 ⁻⁷ mol per mol of silver, and after completion of grain formation, 3 mmol of KI was added per mol of silver for halogen substitution.

After that, washing and desalting were carried out by a conventional method, and a bactericide composed of a mixture of the following compounds [A], [B] and [C] and ossein gelatin were added and redispersed. The obtained emulsion was cubic grains having an average grain size of 0.2 μm and a coefficient of variation of 10%.

[0076]

[Chemical formula 22]

(Preparation of silver halide photographic light-sensitive material) One side of a polyethylene terephthalate support having a thickness of 100 μm, provided with an undercoat layer having a thickness of 0.1 μm on both sides (see Example 1 of JP-A-59-19941). Then, a photosensitive silver halide emulsion layer of the following formulation (1) was coated so that the amount of gelatin would be 2.0 g / m ² and the amount of silver would be 3.2 g / m ² , and then the following formulation (2) the emulsion protective layer was coated so as the amount of gelatin is 1.5 g / m ^2, and also gelatin backing layer of the support surface opposite to the emulsion layer following formulation in (subbing machined) (3) The coating amount was 2.4 g / m ^2, and a backing protective layer having the following formulation (4) was further applied thereon so that the gelatin amount was 1 g / m ² . Formulation (1) (composition of photosensitive silver halide emulsion layer) Gelatin 2.0 g / m ² Silver halide emulsion A Silver amount 3.2 g / m ² Sensitizing dye: Anhydro-5.5'-dichloro-9-ethyl 3,3 ' -Bis (3-sulfopropyl) oxacarbocyanine hydroxy sodium salt 8.0 mg / m ² Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5 -Nitroindazole 10 mg / m ² 1-phenyl-5-mercaptotetrazole 2 mg / m ² Surfactant: saponin 0.1 g / m ² sodium sulfosuccinate isopentyl normal decyl ester 8.0 g / m ² hydrazine derivative (listed in Table 1) 3 x 10 ^-5 mol / m ²

[0078]

[Chemical formula 23]

Formula (3) (backing layer composition)

[0080]

[Chemical formula 24]

Gelatin 2.4 g / m ² Surfactant: Sodium dodecylbenzene sulfonate 50 mg / m ² formulation (4) (Backing protective layer composition) Gelatin 1 g / m ² Matting agent: Monodisperse polymethyl with average particle size 5.0 μm Metaakurito 50 mg / m ² surfactant: sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² hardener: glyoxal 25 mg / m ² hardener: below for H-1 35mg / m ² obtained sample The quality was evaluated according to the test method.

(Sensitivity and gamma) The obtained sample was brought into close contact with a step wedge and exposed to a tungsten light of 3200 ° K for 3 seconds, and then a developing solution and a fixing solution having the compositions shown below were added to Konica Corporation. Company's rapid processing automatic processor GR-2
6SR was processed under the following conditions. Sensitivity is fog density +
3.0 The reciprocal of the exposure dose that gives a transmission density, and the relative value under each condition was determined with the sensitivity of Sample No. 1 as 100.
Further, gamma was obtained from the slope of the characteristic curve in transmission densities 1 to 3. Practically, the gamma is preferably 10 or more.

(Eye enlargement) a) Manuscript preparation Using a scanner SG747 manufactured by Dainippon Screen Co., Ltd. and a new RST system scanner film RSP-3 manufactured by Konica Corporation, a transparent image and a dot% of a person consisting of halftone dots are obtained. The step wedge which changed gradually was created. The screen frequency at this time was 150 lines / inch.

B) Photographing The above document was set on a Fine Zoom C-880F manufactured by Dainippon Screen Co., Ltd. so that the magnification was 120% and exposed. At this time, 95% of the step wedge of the manuscript is 5
The exposure was performed so that it became%. The exposed sample was developed by the method for determining the sensitivity and gamma.

C) Evaluation method Gradation reproducibility of the shadow portion of the sample obtained by adjusting the exposure amount and combining the dot percentages on the small dot side (highlight portion) (hardness of dot collapse) The evaluation was carried out in 5 grades in order from the best one.

(Black spot quality performance test method) An unexposed film was processed as follows, and the processed film was observed with a magnifying power of 50 times, and the one in which no black spot was generated in the halftone dot was the highest. Rank “5”, rank “4”, “3”, “2”, depending on the degree of occurrence of black spots occurring in 2 mm × 2 mm,
It was set to "1". A rank of "2" or lower is a practically problematic level.

The processing conditions are as follows.

Developer Formulation (1) Sodium Bisulfite 40g N-Methyl-p-aminophenol Sulfate 350mg Ethylenediaminetetraacetic acid disodium salt 1g Sodium chloride 5g Potassium bromide 1.2g Trisodium phosphate 75g 5-Methylbenztriazole 250mg 2-Mercaptobenzthiazole 23 mg Benztriazole 83 mg Hydroquinone 29 g Diisopropylaminoethanol 2.3 ml Potassium hydroxide Amount to make the pH of the working solution as shown in Table 1 Water was added at the time of use to make 1 liter.

Further, in order to check the preservability of the developing solution,
The developer (30 liters) was placed in a plastic container having an opening area of 100 m ² and left to stand for 5 days while being freely exposed to air.

Fixer formulation (1) Ammonium thiosulfate (59.5% W / V aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% W / V aqueous solution) 82 g Citric acid (50% W / V) / V aqueous solution) 15.7 g Gluconic acid (50% W / W aqueous solution) 8.55 g Aluminum sulphate (48% W / W aqueous solution) 13 ml Glutaraldehyde 3 g Sulfuric acid The pH of the used solution is 4.6. Finished

Development processing conditions Process Temperature Time Image 38 ° C. 20 seconds Fixing 38 ° C. 20 seconds Water washing Normal temperature 15 seconds Drying 40 ° C. 15 seconds The results are shown in Table 1.

[0092]

[Table 1]

From Table 1, the sample of the present invention is excellent in reproducibility of halftone dots such as stretching, and this effect is particularly remarkable in the sample containing a highly active hydrazine derivative which hardens with a developer having a pH of 11 or less. I understand.

Example 2 (Preparation of silver halide photographic emulsion) An aqueous silver nitrate solution and KBr, KI were prepared so that the silver halide composition was 68 mol% silver chloride, 30 mol% silver bromide and 2 mol% silver iodide. The silver halide grains were grown by mixing by the control double jet method. At this time, the mixture was carried out under the conditions of pH 7.8 and pH 3.0, and immediately before the completion of grain formation, K ₂ IrCl ₆ was added in an amount of 6 × 10 ^-7 mol per mol of silver.

Thereafter, desalting was carried out using modified gelatin treated with phenylisocyanate, and the bactericide of Example 1 and ossein gelatin were added and redispersed. The obtained emulsion was an emulsion composed of cubic grains having an average grain size of 0.25 μm and a coefficient of variation of 10%.

(Preparation of silver halide photographic light-sensitive material) One side of a polyethylene terephthalate support having a thickness of 100 μm, provided with an undercoat layer having a thickness of 0.1 μm on both sides (see Example 1 of JP-A-59-19941). Then, a light-sensitive silver halide emulsion layer having the following formulation (1) was coated so that the amount of gelatin would be 1.8 g / m ² and the amount of silver would be 3.2 g / m ² , and then the same as in Example 1. A sample was obtained by coating the emulsion protective layer, the backing layer and the backing protective layer. Formulation (composition of photosensitive silver halide emulsion layer) Gelatin 1.8 g / m ² Silver halide emulsion A Silver amount 3.5 g / m ² Compound represented by general formula [1] of the present invention Sensitizing dyes shown in Table 1: D1 8.0 mg / m ² : D2 3.0 g / m ² Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5-nitroindazole 10 mg / m ² 1-Phenyl-5-mercaptotetrazole 2 mg / m ² Surfactant: saponin 0.1 g / m ² sodium sulfosuccinate isopentyl normal decyl ester 8.0 g / m ² hydrazine derivative (listed in Table 1) 3 × 10 ^-5 mol / M ² Nucleation accelerator: Compound of Table 2 1.6 × 10 ⁻⁴ mol / m ² Polymer latex P 0.5 g / m ² Hardener H-1 60 mg / m ²

[0097]

[Chemical 25]

The quality of the obtained sample was evaluated according to the following test method.

(Sensitivity and gamma) Same as in Example 1 (Linearity) 21-step test in which linearity correction of the obtained sample was canceled with a scanner SG757 manufactured by Dainippon Screen Co., Ltd. and the net% was changed in 5% increments The pattern was output at a screen frequency of 500 lines / inch. At this time, the laser power was changed and output was performed, and processing was performed with the following developer. At this time, when the transmission density of the 100% halftone area is 4.2, the appropriate exposure is set, and the actual halftone area of the area that originally outputs 50% halftone area is measured and the difference from the setting (50%) is calculated. I asked. The smaller this difference is, the better the linearity is.

Practically, when it is 10% or more, the dot area may change abruptly when linearity correction is performed, which is a serious problem.

The processing conditions are as follows.

Developer Formulation (2) Sodium sulfite 50g 1-Phenyl-4-methyl-hydroxymethyl-3-pyrazolidone 700mg Diethylenetriamine pentaacetic acid 1.5g Boric acid 2g Potassium bromide 5g Potassium carbonate 5g 5-Methylbenztriazole 250mg Benztriazole 83mg Hydroquinone 25 g Potassium hydroxide Amount to make pH of working solution 10.5 At the time of use, water was added to make 1 liter.

The formulation of the fixing solution is the same as that in Example 1. Development condition Process temperature Time image 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Water washing 15 minutes at room temperature Dry 40 ° C. 15 seconds The results are shown in Table 2.

[0104]

[Table 2]

From Table 2, it can be seen that the samples of the present invention are excellent in linearity and generate few black spots.

Example 3 (Preparation of silver halide photographic emulsion) Aqueous silver nitrate solution and NaC
1 and a solution of rhodium hexachloride complex added to the KBr aqueous solution in an amount of 8 × 10 ⁻⁵ mol per 1 mol of silver were mixed in the gelatin aqueous solution by the control double jet method. Desalting was carried out by a usual flocculation method, and ossein gelatin was added and redispersed. The obtained emulsion was silver chlorobromide containing 1 mol% of silver bromide, had an average grain size of 0.13 μm and a coefficient of variation.
The emulsion consisted of 10% cubic grains.

(Preparation of silver halide photographic light-sensitive material) One side of a polyethylene terephthalate support having a thickness of 100 μm, provided with an undercoat layer having a thickness of 0.1 μm (see Example 1 of JP-A-59-19941) on both sides. A photosensitive silver halide emulsion layer of the following formulation (1) was applied so that the amount of gelatin would be 1.8 g / m ² and the amount of silver was 3.5 g / m ^2, and the emulsion protective layer of the formulation (2) Was painted.
Further, a backing layer and a backing protective layer similar to those in Example 1 were applied to obtain a sample. Formulation (composition of photosensitive silver halide emulsion layer) Gelatin 1.8 g / m ² Silver halide emulsion A Silver amount 3.5 g / m ² Compound represented by general formula [1] of the present invention 3.0 mg / m ² Stabilizer: 4-Methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² antifoggant: 5-nitroindazole 10 mg / m ² 1-phenyl-5-mercaptotetrazole 2 mg / m ² surfactant : Saponin 0.1 g / m ² sodium sulfosuccinate isopentyl normal decyl ester 8.0 g / m ² hydrazine derivative: (shown in Table 3) 3 × 10 ^-5 mol / m ² nucleation accelerator: (shown in Table 3) 1.6 × 10 ^-4 mol / m ² polymer latex P 0.5 g / m ² polyethylene glycol (MW = 4000) 30 mg / m ² hardener H-1 60 mg / m ² formulation (2) (emulsion protective layer composition) gelatin 1.8 g / M ² Dye: F-1 40 mg / m ² F-2 20 mg / m ² Matting agent: Silica with an average particle size of 3.5 μm 20 mg / m ² Surfactant: S-2 10 mg / m ² S- 3 2mg / m ² Hardener: Formalin 30mg / m ²

[0108]

[Chemical formula 26]

The quality of the obtained sample was evaluated according to the following test method.

(Sensitivity and gamma) The same as in Example 1 (blank character quality) The obtained sample was measured with a bright room printer P-607 manufactured by Dainippon Screen Co., Ltd. as shown in FIG. 1 of JP-A-2-293736. Image exposure was performed through a different original, development processing was performed under the processing conditions of Example 2, and then the quality of blank characters was evaluated.

Extracted character image quality: As described in JP-A-2-293736, a sticking base / a film on which a line drawing positive image is formed (line drawing original) / a sticking base / a film on which a halftone image is formed (shading) (Dot originals) are stacked in this order and are brought into close contact with the protective layer of each film sample so that the halftone originals overlap face-to-face, and a 50% halftone dot area is placed on the film sample.
Proper exposure to give a halftone dot area of 50% was performed, and when processed as described above, a line drawing original with a character of 30 μm width was reproduced as 5, and a character with a width of 150 μm or more was reproduced as 1 The sensory evaluation was performed in 5 steps. 3 is a practical limit.

The results are shown in Table 3.

[0113]

[Table 3]

From the results shown in Table 3, it can be seen that the samples of the present invention are excellent in the quality of characters to be extracted, are excellent in sensitivity and fog, and suppress the generation of black spots.

[0115]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is super-high contrast, faithfully reproduces an original, has excellent image quality, and has excellent development stability.

Claims (3)

[Claims] 1. A hydrazine derivative and the following general formula [1]:
A silver halide photographic light-sensitive material comprising a compound represented by: [Chemical 1] Wherein, A and B each represent a group of nonmetallic atoms necessary for forming a heterocyclic ring, X ^- represents an anion (e.g. Cl ^-, B
r ⁻ , ClO ₄ ⁻ , CH ₃ SO ₃ ^−, etc.). ] 2. The silver halide photographic light-sensitive material according to claim 1, which contains a compound represented by the following general formula [2] or [3]. [Chemical 2] [In the formula, R ₁ , R ₂ , and R ₃ represent 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. R ₁ ,
A ring can be formed by 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. ] [Chemical 3] [In the formula, Ar represents a substituted or unsubstituted aryl group or a 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. ] 3. The silver halide photographic light-sensitive material according to claim 2, wherein the hydrazine compound according to claim 2 is a compound represented by the following general formula [4]. [Chemical 4] [In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and B represents an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfamoyl group, Represents a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group, or a heterocyclic group, and A ₁ and A ₂
Are both hydrogen atoms or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group. However,
B, A ₂ and the nitrogen atom to which they bind are a partial structure of hydrazone. May be formed. ]