JPH07159916A - Silver halide photogrpahic sensitive material - Google Patents

Abstract

PURPOSE:To prevent fluctuation of sensitivity and lowering of contrast and increase of black spots due to time lapse by incorporating a hydrazine derivative and a specified compound in a silver halide emulsion layer and/or a hydrophilic colloidal. CONSTITUTION:This photosensitive material containing at least one kind of hydrazine derivative in the silver halide emulsion layer and/or the hydrophilic colloidal layer contains one of the compounds represented by formulae I-III in which each of R1 and R2 is optionally substituted alkyl or such aryl; each of X1 and X2 is S, Se, or Te; G is H, OH, SO3M, or NR3R4 and each may be substituted on the o-, m-, and p-positions, preferably, the para position to S; Z comprises an optionally substituted carbon or hetero ring; and R8 is optionally substituted alkyl or aryl, optionally 2-8 C carboxyalkyl, carboxyaryl, alkyl ester, or aryl ester.

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 for printing plate making, and more particularly to a silver halide photographic light-sensitive material used in a process called "return" in a plate making process.

[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 process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultra-high contrast.

The lith-type silver halide photographic light-sensitive material (hereinafter, also simply referred to as "lith-type light-sensitive material") used for infectious development has, for example, an average particle diameter of 0.2 μm, a narrow particle distribution and a well-formed particle shape. And a silver chlorobromide emulsion having a high silver chloride content (at least 50 mol% or more). By processing the lith-type light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, that is, a so-called lith-type developer, an image with high contrast, high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to air oxidation and have extremely poor preservability, it is difficult to keep the development quality constant during continuous use.

A method is known in which a rapid and high-contrast image is obtained without using the lith developer. For example, as disclosed in JP-A-56-106244, a light-sensitive material containing a hydrazine derivative is processed with an alkali developing solution. According to these methods, it is possible to obtain a high-contrast image even by processing with a developing solution having good preservative property and capable of rapid processing.

In these techniques, in order to fully exert the high contrast property of the hydrazine derivative, the hydrazine derivative had to be treated with a developer having a pH of 11.2 or higher. A high pH developer having a pH of 11.2 or higher is more stable than a lith developer when exposed to air, and is more stable than a lith developer, but sometimes the ultrahigh contrast image cannot be obtained due to the oxidation of the developer. . In order to compensate for this drawback, JP-A-63-29751, JP-A-1-
No. 179939, No. 1-179940 and U.S. Pat. No. 4,975,354 disclose a light-sensitive material containing a hydrazine derivative and a nucleation accelerator that cause a high contrast even in a developer having a relatively low pH of less than pH 11.2.

However, in the case of an image forming method in which a light-sensitive material containing such a contrast-increasing agent is processed with a developer having a pH of less than 11.0, sensitization or softening occurs over time, and unexposed areas after development are processed. The current situation is that there is a problem that the sandy fog that occurs, so-called black spots, deteriorates, and satisfactory performance cannot be obtained.

On the other hand, the quality of scanners has been improved in the plate making industry, and high-definition image output of 600 lines / inch or more is becoming widespread. However, in the plate making process, plate making is rarely done directly from the output scanner film, and multiple patterns, character images, etc. are printed and composited on the return film in the plate making process to form the final image for the printing plate. Is normal. At this time, if the scanner photosensitive material that is output with high precision using the conventional return photosensitive material is returned, the problem occurs that halftone dots become thick and faithful reproduction cannot be performed. Therefore, it is desired to provide a reversal light-sensitive material capable of faithfully reproducing a high-definition image.

[0009]

In contrast to the above problems, the object of the present invention is to prevent the sensitivity from changing with time, softening, and increasing black spots even when processed with a developer having a pH of less than 11.0. Another object of the present invention is to provide a return silver halide photographic light-sensitive material capable of faithfully expressing a high-definition image. Still another purpose is sensitivity fluctuation and softening even when continuously processed,
An object of the present invention is to provide a silver halide photographic light-sensitive material for printing plate making in which generation of black spots is suppressed.

[0010]

The above object of the present invention is to provide a silver halide photographic light-sensitive material containing at least one hydrazine derivative in a silver halide emulsion layer and / or a hydrophilic colloid layer. This is achieved by a silver halide photographic light-sensitive material characterized by containing a compound represented by [1] or [2] or [3].

General formula [1] R ₁ -X ₁ -X ₂ -R ₂ [wherein R ₁ and R ₂ represent a substituted or unsubstituted alkyl group or an allyl group, and X ₁ and X ₂ represent S, Represents Se and Te, which may be the same or different. R ₁ , R ₂ , X ₁ and X ₂ may form a ring. More preferably the molecule is symmetrical. ]

[0012]

[Chemical 3]

[In the formula, G may be at any position of ortho, meta, and para, and H, OH, SO ₃ M, NR ₃ R ₄ (M is H, ammonium cation, sodium ion, potassium ion)
Is. More preferably, the position is para with respect to S. More preferably the molecule is symmetrical. R ₃ represents a substituted or unsubstituted alkyl group or an allyl group, R ₄ represents H, O = CR ₅ , O = CR ₆ R ₇ , R ₅ , R ₆ and R ₇ are each H, OH, an alkyl group, an allyl group, a fluoroalkyl group, a carboxylalkyl group, an allyl group, an alkylthioether group, an allylthioether group, a sulfoalkyl group, and a sulfoallyl group. ]

[0014]

[Chemical 4]

[Z includes a substituted or unsubstituted C or a heterocycle. When forming a heterocycle, the heteroatom is preferably a nitrogen atom. The carbon number is preferably 4-8. R ₈ represents a substituted or unsubstituted alkyl group or allyl group. (The carbon number is 2
~ 8 are preferred) represents a carboxyalkyl group, a carboxyallyl group, an alkyl ester group, and an allyl ester group. The present invention will be specifically described below.

The light-sensitive material of the present invention contains a hydrazine derivative represented by the following general formula [H].

[0017]

[Chemical 5]

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, 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 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.

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 a nitrogen atom to which they are bonded.

[0028]

[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 [Ha].

[0034]

[Chemical 7]

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

[0036]

[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, 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.

[0043] 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

[0045]

[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, 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.

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

[0051]

[Chemical 13]

[0052]

[Chemical 14]

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

Specific compounds other than the above are disclosed in JP-A-4-
98239, pages 604 (4) to 607 (7), compound examples H-1 to H-75.

As the hydrazine derivative, the above general formula [H]
In the case of containing halogen, at least one of the nucleation promoting compounds (nucleation promoting agents) described in JP-A-4-98239, page (7), lower left column, line 1 to page (26), lower left column, line 11 is halogen. It is preferably contained in the non-photosensitive layer on the silver halide emulsion layer and / or silver halide emulsion layer side.

Examples of the nucleation accelerator include those represented by the following general formula [Na] or [Nb].

[0059]

[Chemical 15]

In the general formula [Na], R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom, an alkyl group, a substituted alkyl group,
It represents an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. R ₁₁ , R ₁₂ , R
₁₃ can combine with each other to form a ring. Particularly preferred are aliphatic tertiary amine compounds.

These compounds preferably have a diffusion resistant group or a silver halide adsorbing group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and more preferably 300 or more. Examples of preferable adsorption groups include nitrogen-containing heterocyclic groups, mercapto groups, thioether groups, thione groups and thiourea groups.

In the general formula [Nb], R ₂₁ and R ₂₂ each represent a substituted or unsubstituted aryl group, aromatic heterocyclic group or hydrogen atom.

These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. The molecular weight is preferably 120 or more, and particularly preferably 300 or more, in order to have preferable diffusion resistance.

Specific compounds represented by the general formulas [Na] and [Nb] include those shown below.

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

When these are contained in the light-sensitive material, they are contained in a silver halide emulsion layer or a hydrophilic colloid layer adjacent to the silver halide emulsion layer. It is particularly preferably contained in the silver halide emulsion layer.

Next, specific examples of the compound represented by the general formula [1] in the present invention will be given, but the present invention is not limited thereto.

[0070]

[Chemical 19]

[0071]

[Chemical 20]

Next, specific examples of the compound represented by the general formula [2] in the present invention will be given, but the present invention is not limited thereto.

[0073]

[Chemical 21]

[0074]

[Chemical formula 22]

[0075]

[Chemical formula 23]

Specific examples of the compound represented by the general formula [3] in the present invention are shown below, but the present invention is not limited thereto.

[0077]

[Chemical formula 24]

The addition amount of the compounds represented by the above general formulas [1], [2] and [3] is 1 × 10 ⁻⁹ to 1 × per mol of silver.
It is 10 ^-2 mol, preferably 1 x 10 ^{-5 to} 3 x 10 ^-4 mol.

Methanol, water, ethanol, and acetone are preferable as the solvent which may be added in the form of solid dissolved in 6 or liquid.

The light-sensitive material according to the present invention can be developed after exposure by various methods, for example, a commonly used method.

The black-and-white light-sensitive material used in the present invention preferably has at least one conductive layer on the support. Typical methods for forming the conductive layer include a method using an aqueous solution conductive polymer, a hydrophobic polymer and a curing agent, and a method using a metal oxide. For these methods, see, for example, JP-A-3-265842, page (5).
The method described on 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, and the like.
Although any of silver chlorobromide and any silver halide such as silver chloride that is commonly used in ordinary silver halide emulsions can be used, silver chlorobromide or silver chloride containing 50 mol% or more of silver chloride is preferable. .

Monodisperse particles having a coefficient of variation of not more than 15% expressed by (standard deviation of particle diameter) / (average value of particle diameter) × 100 are preferable.

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, pages 25 to 26, page 649, right column to ultraviolet absorbers, page 650, left column 7. Anti-staining agent Page 25 Right column Page 650 Left column-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 Same as above As the support that 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.

[0087]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Latex Lx-A) 1.0 kg of gelatin was added to 60 liters of water.
A mixture of 0.01 kg of sodium dodecylbenzene sulfonate and 0.05 kg of ammonium persulfate was stirred at a liquid temperature of 60 ° C. under a nitrogen atmosphere while a mixture of styrene 3.0 kg, methyl methacrylate 3.0 kg and ethyl acrylate 3.2 kg and 2-
Sodium acrylamido-2-methylpropanesulfonate (0.8 kg) was added over 1 hour, the mixture was stirred for 1.5 hours, steam distilled for 1 hour to remove residual monomers, and then cooled to room temperature. Adjusted to 6.0. The obtained latex liquid was made up to 75 kg with water. As described above, a monodisperse latex having an average particle size of 0.1 μm was obtained.

(Emulsion preparation) A silver nitrate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × rhodium hexachloride complex.
A solution added to 10 ^-5 mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate, and then desalted according to a conventional method to obtain a cubic crystal having a grain size of 0.13 μm and 1 mol% of silver bromide. ,
A monodisperse silver chlorobromide emulsion was obtained.

During sulfur sensitization of this emulsion by a conventional method, the compounds of the present invention shown in Table 1 were added, and 6-methyl-4-hydroxy-1,3,3a, 7 tetrazaindene was added as a stabilizer. Was added. Further, the following compounds were added, and then the following additives were added to prepare an emulsion coating solution.

Emulsion coating solution Hydrazine derivative (shown in Table 1) 1 × 10 ⁻⁴ mol / mol Ag p-nonylphenol / ethylene oxide 35 mol adduct 100 mg / m ² (C ₅ H ₁₁ N-CH ₂ CH ₂ OCH ₂ CH ₂ ) ₂ S 1 × 10 ^-3 mol / molAg Potassium bromide 5 mg / m ² 2,5-Dimethyl-4-isothiazolin-3-one 1 mg / m ² 0.5N sodium hydroxide solution Adjusted to pH 5.6 saponin (20% ) 0.5 cc / m ² sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² 1-phenyl-5-mercaptotetrazole 2 mg / m ² 2,5-di (carboxymethylthio) -1,3, 4-thiadiazole 10 mg / m ² 3,3,3 ′, 3′-tetramethyl-5,6,5 ′, 6′-tetrahydroxy-1,1′-spirobiindane 6 mg / m ² latex Lx-A 0.5 g / m ² styrene - maleic acid copolymer (thickener) 90 mg / m ² in addition, when the emulsion coating, the amount of gelatin was adjusted to 1.2 g / m ²

Next, an emulsion protective layer coating solution, a backing layer coating solution, and a backing protective layer coating solution were prepared with the following compositions.

[0093]Emulsion protective layer coating solution Gelatin 1.1 g / m² Compound (b) 40mg / m² Compound (d) 100 mg / m² Spherical monodisperse silica (8μm) 20mg / m² 〃 (3μm) 10mg / m² Gallic acid allyl ester 100mg / m² Compound (a) 1 mg / m² Sodium oxalate adjusted to pH 5.8 Latex Lx-A 0.5g / m² Styrene-maleic acid copolymer (thickener) 50mg / m² Formaldehyde (hardening agent) 10 mg / m² Backing layer coating liquid Gelatin 1.0 g / m² Compound (c) 80mg / m² Compound (d) 15 mg / m² Compound (e) 150mg / m² Calcium chloride 0.3mg / m² Saponin (20% aqueous solution) 0.6cc / m² Sodium oxalate adjusted to pH 5.5 Latex (m) 300mg / m² 5-methylbenzotriazole 10mg / m² 5-nitroindazole 20mg / m² Polyethylene glycol (Molecular weight 1540) 10mg / m² Styrene-maleic acid copolymer (thickener) 45mg / m² Glyoxal (hardening agent) 4 mg / m² Compound (n) 80mg / m² Backing protective layer coating liquid Gelatin 1.18g / m² Compound (a) (1% aqueous solution) 2 ml / m² Compound (c) 20mg / m² Compound (d) 4 mg / m² Compound (e) 50mg / m² Spherical polymethylmethacrylate (4μm) 25mg / m² Sodium chloride 70mg / m² Compound (a) 1 mg / m² Glyoxal 22mg / m² Bisvinylsulfonyl methyl ether (hardener) 5 mg / m^Two

[0094]

[Chemical 25]

[0095]

[Chemical formula 26]

[0096]

[Chemical 27]

Each coating solution prepared as described above was applied to the emulsion side by undercoating shown in JP-A-59-19941 to obtain a thickness of 10
After applying corona discharge at 10 W / m ² · min to the backing surface side of 0 μm polyethylene terephthalate base, use the roll-fit coating pan and air knife with the following composition so that the coating amount will be 10 cc / m ^2. Applied and dried.

Drying was performed at 90 ° C., and overall heat transfer coefficient was 25 kcal (m ²
・ Hr ・ ° C) parallel flow drying condition for 30 seconds, then 140 ° C ・
It took 90 seconds. The thickness of the layer after drying was 1 μm, and the surface specific resistance of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0099]

[Chemical 28]

Ammonium sulfate 0.5 g / liter Polyethylene oxide compound (average molecular weight 600) 6 g / liter Curing agent 12 g / liter

[0101]

[Chemical 29]

On this base, the emulsion layer and the emulsion protective layer were sequentially coated from the side closer to the support as the emulsion surface side in this order while maintaining the temperature at 35 ° C. while adding a hardener solution by a slide hopper system, and then cold air was applied. After passing through the set zone (5 ° C.), a backing layer and a backing protective layer were coated on the side opposite to the emulsion surface with a slide hopper while adding a hardening agent, and set with cold air (5 ° C.). The coating liquid exhibited sufficient setting properties when it passed through each setting zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the backing surface side, it was conveyed in a state in which there was no contact with the roller or the like until winding up. The coating speed at this time was 120 m / min.

(Drying conditions) After setting, the product was dried with a dry air at 30 ° C. until the weight ratio of water / gelatin reached 800%, and then 800 to 20.
Dry 0% with 35 ° C (30%) dry air, apply the air as it is, and 30 seconds after the surface temperature reaches 34 ° C (it is considered that the drying is completed), use 48 ° C / 2% air. It was dried for 1 minute. At this time, the drying time is from start of drying to water / gelatin ratio of 800%.
0 second, 35% from 800% to 200%, 5 seconds from 200% to the end of drying.

This light-sensitive material was wound at 23 ° C. and 40%, then cut under the same environment, and placed in a barrier bag conditioned for 3 hours at 40 ° C.
After conditioning the humidity at 10% for 8 hours, it was sealed together with the thick paper which was regulated at 23 ° C. and 40% for 2 hours to obtain a fresh sample. Further, as a raw storability substitute test of the film, the film was forcibly deteriorated by leaving it in an environment of humidity 50 ° C. and 50% RH for 3 days.

The coated silver amount of the light-sensitive material produced as described above was 3.5 g / m ² .

The sample produced as described above was output with a scanner SG-747 (manufactured by Dainippon Screen Co., Ltd.) and a high-definition (600 lines / inch) halftone dot image was used as an original for printer P-627GM (Dainippon Contact-exposure using a screen (manufactured by K.K.), rapid processing automatic processor GR-26S manufactured by Konica.
R was developed according to the following processing conditions. (45 second processing) (Development processing conditions) Process temperature Time Development 38 ℃ 12 seconds Fixing 35 ℃ 10 seconds Water washing 10 minutes normal temperature 10 seconds Drying 50 ℃ 13 seconds Developer formulation Sodium sulfite 55g Potassium carbonate 40g Hydroquinone 24g 4-Methyl-4-hydroxy Methyl-1-phenyl-3-0.9g Pyrazolidone (Dimeson S) Potassium bromide 5g 5-Methylbenzotriazole 0.13g 1-Phenyl-5-mercaptotetrazole 0.02g Boric acid 2.2g Compound VIII-5 100mg Compound IX-2 300mg Diethylene glycol 40g Add water to make 1 liter and add sodium hydroxide to pH
Adjust to = 10.5.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5 W / V% aqueous solution) 240 cc Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium oxalate dihydrate 2.0 g (Composition B) Pure Water (ion-exchanged water) 17cc Sulfuric acid (50W / v% aqueous solution) 4.7g Aluminum sulphate (Al2o3 equivalent content is 8.1W / V% aqueous solution) 26.5g Dissolve composition A and composition B in 500cc of water in this order when used. 1
Finished to liters. The pH was adjusted to 4.8 with acetic acid.

At this time, the appropriate exposure amount was the exposure amount at which the density of the inverted (blackened) image portion with respect to the non-image portion of the original became 4.6, and the blackened area of the halftone dot image at this exposure amount was measured. The density was measured by ortho light using a PDA-65 densitometer (manufactured by Konica Corp.) and the dot area was measured using X-Rite 361T. The halftone dot area of the manuscript was 43.8%.

The developed sample thus obtained was measured with a Konica digital densitometer PDA-65, and gamma was represented by the tangent of densities of 0.1 and 2.5. A gamma value of less than 6 is unusable, and a gamma value of 6 or more and less than 10 still has insufficient hardness. Only when the gamma value is 10 or more, a super-high contrast image will be obtained, and it will be practically usable.

The black spots in the unexposed area were also evaluated using a magnifying glass of 40 times. The highest rank is "5" when black spots are not generated at all, and the rank is gradually lowered to "4", "3", "2", "1" according to the degree of occurrence of black spots. It shall be evaluated. Rank "1" and "2"
The black spots are also levels that are not practically preferable.

The results are also shown in Table 1.

[0112]

[Table 1]

From the results shown in Table 1, the sample of the present invention had a pH of 11.0.
It can be seen that even if the treatment is performed with a developing solution of less than 1, the contrast is high and the generation of black spots is suppressed. Also, it can be seen that a high-definition image can be faithfully expressed with little weight gain. It can also be seen that the generation of black spots is suppressed even with the passage of time.

Example 2 The sample prepared in Example 1 was used and treated under the following conditions.

(Development Processing Conditions) Process Temperature Time Development 38 ° C. 12 sec Fixing 35 ° C. 10 sec Water wash 10 ° C. normal temperature 10 sec Dry 50 ° C. 13 sec Total 45 sec Each process time includes so-called transit time to the next process.

For replenishment, the developer is 150 ml / m ² , and the fixer is 190 ml /
The same solution as the new solution was used for m ² .

Of two sets of samples exposed in the same manner as in Example 1, one set was treated with a developing solution of a new solution, and the other set was 1 /
The film exposed to 5 was developed using a fatigue developer obtained by developing 30 m ^{2 of} the film.

The developed sample thus obtained was measured with a PDA-65 densitometer (manufactured by Konica Corporation). The sensitivities in the table are relative sensitivities when the sensitivity of Sample No. 1 at a concentration of 3.0 is 100.

The results of evaluation as in Example 1 are shown below.

[0120]

[Table 2]

From the results shown in Table 2, it can be seen that the sensitivity is not deteriorated even in the case of continuous treatment, the soft tone is not generated, and the black spots are good.

[0122]

EFFECTS OF THE INVENTION According to the present invention, even when processed with a developer having a pH of less than 11.0, it is possible to prevent the sensitivity from changing with time, softening and increase of black spots, and to faithfully express a high-definition image. Even in such a case, it was possible to provide a silver halide photographic light-sensitive material for printing plate making in which softening of sensitivity varied and generation of black spots was suppressed.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one hydrazine derivative in a silver halide emulsion layer and / or a hydrophilic colloid layer, containing a compound represented by the following general formula [1]. A silver halide photographic light-sensitive material characterized by the above. Formula (1) R ₁ -X ₁ -X ₂ -R ₂ [wherein, R _1, R ₂ is a substituted or unsubstituted alkyl group, an allyl group, X _1, X ₂ is S, Se, Te And may be the same or different. R ₁ , R ₂ , X ₁ and X ₂ may form a ring. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein the general formula [1] according to claim 1 is a compound represented by the following general formula [2] or [3]. [Chemical 1] [In the formula, G may be at any position of ortho, meta, and para, and is H, OH, SO ₃ M, or NR ₃ R ₄ (M is H, ammonium cation, sodium ion, potassium ion). ]
R ₃ represents a substituted or unsubstituted alkyl group, or allyl group, R ₄ is H, represents _{O = CR 5, O = CR} 6 R 7, R 5, R 6, R 7
Represents H, OH, an alkyl group, an allyl group, a fluoroalkyl group, a carboxylalkyl group, an allyl group, an alkylthioether group, an allylthioether group, a sulfoalkyl group, and a sulfoallyl group, respectively. ] [Chemical 2] [Z includes a substituted or unsubstituted C or a heterocycle. R ₈ is a substituted or unsubstituted alkyl group, allyl group, carboxyalkyl group, carboxyallyl group, alkyl ester group,
Represents an allyl ester group. ]