JPH075611A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material superior in scratch blackening pressure resistance and small in tendency to soft tone and deterioration of sensitivity. CONSTITUTION:The silver halide photographic sensitive material is characterized by containing a hydrazine derivative, further a nucleation promoter and a polymer latex stabilized with a gelatin in at least one silver halide emulsion layer and/or another hydrophilic colloidal layer on a support.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material having a silver halide light-sensitive layer on a support, and more particularly to a silver halide photographic light-sensitive material capable of obtaining high contrast.

[0002]

2. Description of the Related Art Conventionally, a photolithography process includes a process 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 in ultra-high contrast.

The lithographic silver halide photographic 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-shaped particle shape, and a high silver chloride content (at least 50 mol). % Or more) of silver chlorobromide emulsion.
By treating this lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, a high contrast,
Images with high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to aerial oxidation, their preservative properties are extremely poor.
It is difficult to keep the development quality constant during continuous use. There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in JP-A-56-106244, a silver halide photographic light-sensitive material containing a hydrazine derivative is treated with an alkali developing solution. According to these methods, it is possible to obtain a high-contrast image by processing with a developing solution which has good preservability and is capable of rapid processing.

In these techniques, the hydrazine derivative had to be treated with a developer having a pH of 11.2 or higher in order to fully exert the high contrast property. In a high pH developer having a pH of 11.2 or higher, the developing agent is easily oxidized when exposed to air. It is more stable than the lith developer, but due to the oxidation of the developing agent, an ultrahigh contrast image may not be often obtained.

In order to make up for this drawback, Japanese Patent Laid-Open No. 63-29751
JP-A 1-179939, JP-A 1-179940 and U.S. Pat.
No. 5,354, etc. disclose a silver halide photographic light-sensitive material containing a hydrazine derivative and a nucleation accelerator which bring about a high contrast even in a developer having a relatively low pH of less than 11.2. On the other hand, it is known in the art that a polymer latex is contained in the emulsion layer and / or other hydrophilic colloid layer constituting the light-sensitive material in order to improve the scratch resistance of the silver halide photographic light-sensitive material.

However, in a silver halide photographic light-sensitive material containing a hydrazine derivative and a nucleation accelerator which produce a high contrast even in a developer having a relatively low pH of less than pH 11.2 as described above, resistance to blackening pressure due to scratches is improved. If a large amount of polymer latex, for example, 0.5 g / m ² or more is added, there is a problem in that the tone becomes soft and the sensitivity is lowered.

Further, these problems are apt to occur remarkably when the above-mentioned light-sensitive material is rapidly processed within a total processing time (Dry to Dry) of 60 seconds or less.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material which is excellent in resistance to blackening pressure due to scratches and which is less likely to cause softening and decrease in sensitivity.

[0010]

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

1. In a silver halide photographic light-sensitive material containing a hydrazine derivative in at least one silver halide emulsion layer and / or other hydrophilic colloid layer on a support, said silver halide emulsion layer and / or other hydrophilic colloid layer A silver halide photographic light-sensitive material characterized by containing a nucleation accelerator therein and a gelatin-stabilized polymer latex in the silver halide emulsion layer and / or other hydrophilic colloid layer. 2. The silver halide photographic light-sensitive material according to the above 1, wherein the silver halide emulsion comprises silver halide containing 50 mol% or more of silver chloride. The present invention will be described in detail below.

The hydrazine derivative used in the present invention preferably has the following general formula [H].

[0013]

[Chemical 1]

[0014]

[Chemical 2]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, 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 hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Alternatively, it represents a heterocyclic oxy group, and R ₁ and R ₂ may form a ring together with a nitrogen atom. When n = 2, R ₁
And R ₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Represents a group. However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Shall represent a group. R ₃ represents an alkynyl group or a saturated heterocyclic group.

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

More specifically, A is an aryl group (eg, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.). Represents

R ₁ and R ₂ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl,
Pentenyl, pentadienyl, etc.), alkynyl group (eg, propargyl, butynyl, pentynyl, etc.), aryl group (eg, phenyl, naphthyl, cyanophenyl,
Methoxyphenyl, etc.), heterocyclic groups (eg, pyridine,
Unsaturated heterocyclic groups such as thiophene and furan and saturated heterocyclic groups such as tetrahydrofuran and sulfolane), hydroxy groups, alkoxy groups (eg, methoxy, ethoxy,
Benzyloxy, cyanomethoxy etc.), alkenyloxy group (eg allyloxy, butenyloxy etc.), alkynyloxy group (eg propargyloxy, butynyloxy etc.), aryloxy group (eg phenoxy, naphthyloxy etc.) or heterocyclic oxy Represents a group (eg, pyridyloxy, pyrimidyloxy, etc.), n
When = 1, R ₁ and R ₂ together with the nitrogen atom may form a ring (eg, piperidine, piperazine, morpholine, etc.).

However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, alkynyl group, saturated heterocyclic group, hydroxy group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group or hetero. It represents a ring oxy group. Specific examples of the alkynyl group and the saturated heterocyclic group represented by R ₃ include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Of these substituents, the sulfonamide group is preferred.

In each general formula, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in non-moving photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more and 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 and an alkylphenoxy group. You can

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108 such as thiourea group, thiourethane group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.

H of --NHNH-- in the general formulas [A] and [B], that is, the hydrogen atom of hydrazine, is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl, trifluoroacetyl, It may be substituted with a substituent such as ethoxycarbonyl) and an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.), and the compounds represented by the general formulas [A] and [B] include such compounds.

More preferred compounds in the present invention are compounds of the general formula [A] when n = 2, and compounds of the general formula [B].
Is a compound of.

In the compound of n = 2 in the general formula [A],
R ₁ and R ₂ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, or an alkoxy group, and R ₁ and R ₂
At least one of them is an alkenyl group, an alkynyl group,
Compounds representing a saturated heterocyclic group, a hydroxy group, or an alkoxy group are more preferable.

Typical compounds represented by the above general formulas [A] and [B] are shown below. However, as a matter of course, the specific compounds of the general formulas [A] and [B] that can be used in the present invention are not limited to these compounds.

Specific compound examples

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

The gelatin-stabilized polymer latex that can be used in the present invention is characterized in that the surface and / or the inside of the polymer latex is dispersion-stabilized with gelatin. It is particularly desirable that the polymer constituting the latex and gelatin have some kind of bond. In this case, the polymer and gelatin may be bound directly or may be bound via a crosslinking agent.

The gelatin-stabilized polymer latex of the present invention is prepared after the polymerization reaction of the polymer latex is completed.
It can be obtained by adding a gelatin solution to the reaction system and reacting. It is preferable to react the polymer latex synthesized in a surfactant with gelatin using a crosslinking agent. Further, it can be obtained by a method in which gelatin is present during the polymerization reaction of the polymer, which gives more preferable results than the above method. Further, in this case, it is preferable not to use a surfactant during the polymerization reaction of the polymer, but when the surfactant is used, its addition amount is 0.1 to 3.0%, particularly preferably 0.1 to 1.5% based on the polymer component. . The present inventor has found that, in the process of continuing to improve the physical properties of the light-sensitive material, there is a specific boundary in the ratio of the added amounts of gelatin and latex.

The ratio of gelatin to polymer at the time of synthesis is 1:
100 to 2: 1 is preferable, and 1:50 to 1: is particularly preferable.
It is 2.

The preferred range of the average particle size of the gelatin-stabilized polymer latex used in the present invention is 0.00.
It is 5 to 1 μm, preferably 0.02 to 0.5 μm.

Examples of the gelatin-stabilized polymer latex of the present invention include those described in US Pat. No. 2,772,166.
3,325,286, 3,411,911, 3,311,912, 3,52
No. 5,620, Research Disclosure
DISCLOSURE) No. 195 19551 (July 1980), etc., and hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters, and styrene.

The polymer latex portion of the polymer latex stabilized with gelatin preferably used in the present invention is a homopolymer of a metaalkyl acrylate such as methyl methacrylate or ethyl methacrylate, a homopolymer of styrene, or a metaalkyl acrylate. Copolymer of styrene with acrylic acid, N-methylol acrylamide, glycidol methacrylate, etc., homopolymer of alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or copolymer of alkyl acrylate with acrylic acid, N-methylol acrylamide, etc. Polymers (preferably up to 30% by weight of copolymerization components such as acrylic acid), butadiene homopolymers or butadiene and styrene, butoxymethyl acrylamide, acrylic acid 1 Above, and a copolymer of vinylidene chloride - methyl acrylate - like terpolymer acrylic acid.

When binding to gelatin via a crosslinking agent, the monomers constituting the polymer latex include
Carboxyl group, amino group, amide group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, active ester group, methylol group, cyano group, acetyl group,
It is desirable to include those having a reactive group such as an unsaturated carbon bond. Further, when a cross-linking agent is used, those used as a cross-linking agent for ordinary gelatin can be used. For example, aldehyde type, glycol type,
Crosslinking agents such as triazine-based, epoxy-based, vinylsulfone-based, oxazoline-based, methacrylic-based, and acrylic-based crosslinking agents can be used. Furthermore, in order to further enhance the dispersion stability of the gelatin-stabilized polymer latex of the present invention, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof can be used as a monomer constituting the polymer latex. The amount of the above-mentioned monomer added is preferably 0.5 to 20% by weight based on the total weight of the constituents.

Examples of gelatin used for stabilizing the latex of the present invention include gelatin and gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used in combination.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bulletin of Society of Japan (Bull.Soc.Sci.Phot.Japan) No. 16, page 30 (196
You may use the acid-processed gelatin as described in 6),
Also, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used. Examples of the gelatin derivative include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones, vinyl sulfonamides, maleinimide compounds, polyalkyleonoxides, and epoxy compounds in gelatin. What is obtained by reacting is used. Specific examples thereof are U.S. Patents 2,614,928 and 3,132,9.
45, 3,186,846, 3,312,553, British Patent 861,41
No. 4, No. 1,033,189, No. 1,005,784, Japanese Patent Publication No. 42-26845
No. etc.

As the protein, albumin, casein,
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, a sulfuric acid ester of cellulose, or as the sugar derivative, sodium alginate or a starch derivative may be used in combination with gelatin.

The gelatin-stabilized polymer latex used in the present invention may be added to at least one hydrophilic colloid layer, but it may be a photosensitive hydrophilic colloid layer and / or a photosensitive hydrophilic colloid layer. A preferable result is obtained when it is added to the non-photosensitive hydrophilic colloid layer on the side. It may be contained on only one side of the support, or may be contained on both sides. A conventionally known latex may be added to the layer to which the latex of the present invention is added and / or not added. When included on both sides of the support, the type and / or amount of polymer latex included on each side may be the same or different.

The amount of the polymer latex of the present invention added is
In order to suppress the blackening pressure due to scratches,
0.5 g / m ² or more is required, preferably 0.7 to 3.0 g / m
^{Is 2} .

Next, some specific examples of the latex that can be used in the present invention are shown. The specific examples of the latex shown in the present specification also represent a latex having any composition ratio of the latex composed of the constituent components. Of course, the specific examples of the latex shown here are typical examples of the latex that can be used, and it goes without saying that the constituent components (not only the composition ratio) of the latex used in the present invention are not limited to these specific examples. Yes.

[0045]

[Chemical 7]

[0046]

[Chemical 8]

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

[0051]

[Chemical 13]

Examples of the nucleation accelerator used in the present invention include amine compounds, hydrazine compounds, quaternary onium salt compounds and carbinol compounds, with amine compounds and carbinol compounds being preferred. Examples of these nucleation accelerators include those described in JP-A-4-56749, JP-A-63-124045 and JP-A-62-187340. These compounds preferably have a diffusion resistance or a silver halide adsorption group in the molecule. Other specific examples include the compounds described in the following patents. Japanese Patent Application 3-29
Compounds described in 5926, 3-293366, 3-286619, 4-33451 and the like.

More specifically, the following nucleation accelerators are listed, but the present invention is not limited thereto.

As compounds described in JP-A-4-56949

[0055]

[Chemical 14]

[0056]

[Chemical 15]

[0057]

[Chemical 16]

And the like.

The silver halide emulsion used in the present invention (hereinafter referred to as "silver halide emulsion or simply emulsion") contains silver chloride containing 50 to 100 mol% of silver chloride, silver chloroiodobromide and salt. Although silver bromide can be used, silver chlorobromide or silver iodobromide containing silver chloride is preferable.

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

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention.

For example, in the silver halide photographic emulsion and backing layer used in the present invention, various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents,
A development inhibitor, an ultraviolet absorber, an anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, the silver halide photographic emulsion and the backing layer of the present invention may contain a polymer latex other than the present invention.

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, and polyolefin are coated. paper,
Examples thereof include glass and metal. These supports are subjected to a surface treatment if necessary.

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

Additive type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic Agent, page 27 Id. To process the silver halide photographic light-sensitive material of the present invention, for example, TH James, The Theory of the Photographic Process, Fourth Edition (The Theory of
the Photographic Process, Fourth Edition) No. 291-33
Page 4 and the Journal of the American Chemical Soci
ety) Volume 73, page 3,100 (1951), and the developers can be effectively used in the present invention.

These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination.

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

The developer used in the present invention has a pH of 10.0 to 11.
2 is preferable. If the pH is less than 10.0, the contrast becomes insufficient, and if the pH exceeds 11.2, black spots are significantly deteriorated.

In addition, the developer includes an inorganic development inhibitor such as bromcali and an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine, and 1-phenyl-5-mercaptotetrazole. Agents, metal ion scavengers such as ethylenediamine tetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxides, sodium alkylaryl sulfonates, natural saponins, surface active agents such as sugars or alkyl esters of the above compounds Agent,
It is optional to add a hardening agent such as glutaraldehyde, formalin and glyoxal, and an ionic strength adjusting agent such as sodium sulfate.

The developer used in the present invention may contain glycols such as diethylene glycol and triethylene glycol as an organic solvent. Further, it is preferable not to include the alkanolamines disclosed in JP-A-56-106244.

[0071]

EXAMPLES Examples of the present invention will be specifically shown below, but it goes without saying that the present invention is not limited to these examples.

Example 1 (Synthesis of Comparative Latex A) A solution prepared by adding 0.01 kg of sodium dodecylbenzenesulfonate and 0.05 kg of ammonium persulfate to 40 liters of water was stirred at a liquid temperature of 60 ° C. under a nitrogen atmosphere. ) Styrene 3.0 kg (a) Methyl methacrylate 3.0 kg and (c) Ethyl acrylate 3.2 kg and (d) 2-acrylamido-2-methylpropanesulfonic acid
Add 0.8kg over 1 hour, then stir for 1.5 hours and then add 1 more
After steam distillation to remove residual monomer, cool to room temperature and adjust the pH to 6.0 with sodium hydroxide.
Adjusted to. The obtained latex liquid was made up to 55 kg with water. As described above, a monodisperse latex having an average particle size of 0.11 μm was obtained.

(Latex Lx-8) 1.0 kg of gelatin in 60 liters of water sodium dodecylbenzenesulfonate
(A) Styrene under a nitrogen atmosphere while stirring at a liquid temperature of 60 ° C in a liquid containing 0.01 kg and 0.05 kg of ammonium persulfate.
3.0 kg, (a) methyl methacrylate 3.0 kg, and (c)
After adding a mixed solution of 3.2 kg of ethyl acrylate and 0.8 kg of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid over 1 hour, stirring for 1.5 hours and then steam-distilling for 1 hour to remove residual monomers, After cooling to room temperature, the pH was adjusted to 6.0 with ammonia. 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.

(Latex Lx-17) A solution prepared by adding 0.01 kg of sodium dodecylbenzenesulfonate and 0.05 kg of ammonium persulfate to 40 liters of water while stirring at a liquid temperature of 80 ° C., under a nitrogen atmosphere, 9.3 kg of (a) ethyl acrylate. ,
(B) Reaction product of epichlorohydrin and acrylic acid 0.4k
g and (c) A mixture of 0.3 kg of acrylic acid was added over 1 hour, then stirred for 1.5 hours, then 1.0 kg of gelatin and 0.005 kg of ammonium persulfate were added and stirred for 1.5 hours. After completion of the reaction, further 1 hour After steam distillation to remove residual monomers, cool to room temperature and then use ammonia to adjust the pH.
Was adjusted to 6.0. The obtained latex liquid was made up to 55 kg with water. As described above, a monodisperse latex having an average particle size of 0.12 μm was obtained.

(Preparation of silver halide photographic emulsion A) A silver chloroiodobromide emulsion (70 mol% of silver chloride, silver iodide) was prepared by the simultaneous mixing method.
0.1 mol%) was prepared. The mixture during the K ₂ IrCl ₆ was per mole silver 8 × 10 ^-7 mol, and Na ₃ RhCl ₄ 1 × 10 ^-7 mol was added. The obtained emulsion was an emulsion composed of cubic monodisperse grains (coefficient of variation 10%) having an average grain size of 0.20 μm. SD-
After adding 8 mg / m ^{2 of} 1, 1 was washed with water and desalted by a conventional method.
Thereafter, a mixture of the compounds [A], [B] and [C] was added, followed by gold sulfur sensitization to obtain an emulsion A.

[0076]

[Chemical 17]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On the undercoat layer, a silver halide emulsion layer having the following formulation (1) was used, in which the amount of gelatin was 1.8 g / m ² and the amount of silver was 3.2 g / m ^2.
And an emulsion protective layer of the following formulation (2) so that the amount of gelatin will be 1.0 g / m ^2, and on the other undercoat layer on the opposite side. Applies a backing layer according to the following formulation (3) so that the amount of gelatin becomes 2.0 g / m ² , and further a backing protective layer of the following formulation (4) so that the amount of gelatin becomes 1 g / m ² . A sample was obtained by applying it to the.

Formulation (1) (Silver Halide Emulsion Layer Composition) Gelatin Amount of 1.8 g / m ² as emulsion layer Silver Halide Emulsion A Silver amount 3.2 g / m ²

[0079]

[Chemical 18]

Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5-nitroindazole 10 mg / m ² Compound (d) 5 mg / m ² Interface Activator: saponin 0.1g / m ²

[0081]

[Chemical 19]

[0082]

[Chemical 20]

Formulation (3) (backing layer composition)

[0084]

[Chemical 21]

Gelatin 2.4 g / m ² Surfactant: Saponin 0.1 g / m ² : S-1 6 mg / m ² Colloidal silica 100 mg / m ² Formulation (4) [Backing protective layer composition] Gelatin 1 g / m ² matting agent average particle size: 3.5μm monodisperse polymethyl methacrylate a cleat 40 mg / m ² surfactant: ^S-2 10mg / m 2 hardener: glyoxal 35 mg / m ² [surrogate blackening pressure by scratches] obtained The sample is cut into 50 cm x 60 cm, and the plate-making camera Auto Companica 690D manufactured by Dainippon Screen Mfg. Co., Ltd. is stored in a dark room.
It was attached to a vacuum board of X, adhered in vacuum, rubbed with an accessory rubber roller 20 times, and then removed without exposing. Then, processing was carried out under the following conditions with an automatic processor GR-26SR for rapid processing manufactured by Konica Corp., in which a developing solution and a fixing solution having the compositions shown below were added. The blackening pressure due to scratches of the obtained sample was visually evaluated on a scale of 1 to 5.

5: No blackening pressure at all 4: Very fine blackening pressure slightly generated 3: Fine blackening pressure slightly generated 2: Thick blackening pressure partially occurred 1: Thick blackening pressure Is generated on the whole, and if it is less than 3, it is a practically problematic level.

[Evaluation of Photographic Performance] A wedge was closely adhered to the obtained sample, which was exposed for 10 ⁻⁶ seconds with a He—Ne laser, and a developing solution and a fixing solution having the compositions shown below were added thereto. ) A rapid processing automatic processor GR-26SR manufactured by the same company was used under the following conditions.

The density of the obtained sample was measured with an optical densitometer, Konica PDA-65, and the sensitivity of sample No. 1 no density 2.5 was 100.
The relative sensitivity is shown, and gamma is displayed with the tangent of the densities of 0.1 and 2.5. If the gamma value is less than 8.0, the contrast becomes insufficient and it can be used.

[Developer composition 1] Potassium sulfite 50 g Hydroquinone 20.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 2.0 g Potassium carbonate 12.0 g Potassium bromide 5.0 g 5-Methylbenzotriazole 0.3 g Diethylene glycol 25.0 g Compound (d) 0.1 g Water was added to make 1 liter, and pH was adjusted to 10.4 with potassium hydroxide.

Fixer formulation Ammonium thiosulfate (72.5% W / V aqueous solution) 200 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Pure water (ion exchanged water) 17 ml Sulfuric acid ( Aqueous solution of 50% W / V) 2.0 g Aluminum sulphate (Aqueous solution containing 8.1% W / V in terms of Al ₂ O ₃ ) 8.5 g The fixing solution was finished to 1 liter and used. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) The time includes the time for wading.

(Process) (Temperature) (Time) Development 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Washing 30 ° C. 10 seconds Drying 50 ° C. 13 seconds Total 45 seconds Table 1 shows the structural formula of the compound (d) and the results. .

[0093]

[Chemical formula 22]

[0094]

[Table 1]

From the results shown in Table 1, it is understood that the samples of the present invention have no deterioration in sensitivity and gamma and are excellent in blackening pressure due to scratches.

Example 2 (Emulsion preparation) 8 × 10 ^-5 mol / Ag of rhodium hexachloride complex was added to a silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide.
The solution, which was added so that it became mol, was added at the same time to the gelatin solution while controlling the flow rate, and after desalting according to the usual method, the particle size was 0.13.
A cubic monodisperse silver chlorobromide (99 mol% silver chloride) emulsion was obtained.

This emulsion was subjected to sulfur sensitization by a conventional method, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and then the following additives were added to apply emulsion. Solution, then emulsion protective layer coating solution, backing layer coating solution,
A backing protective layer coating solution was prepared with the following composition.

(Preparation of Emulsion Coating Solution) Silver Halide Emulsion 3.0 g / m ² as Silver Amount Gelatin 1.2 g / m ² as Emulsion Coating Solution hydrazine derivative H-4 of the present invention 10 mg / m ² Hydrazine derivative of the present invention H-15 7.5 mg / m ² Nucleation accelerator (19) 40 mg / m ² Compound (e) 7.5 mg / m ² Saponin (20%) 0.5 ml / m ² 5-nitroindazole 10 mg / m ² Hydroquinone 50 mg / m ² 1-Phenyl-5-mercaptotetrazole 5 mg / m ² Latex polymer of the present invention and comparison Amount shown in Table 2 Styrene-maleic acid copolymerizable polymer (thickener) 90 mg / m ² (emulsion protection Layer coating solution) Gelatin 0.7 g / m ² compound (f) 40 mg / m ² compound (g) 100 mg / m ² Spherical monodisperse silica (particle size 8 μm) 20 mg / m ² 〃 (particle size 3 μm) 10 mg / m ² Interface Activator S-3 (synonymous with Example 1)
5 mg / m ² Citric acid adjusted to pH 5.8 Inventive and comparative latex polymers Amount shown in Table 2 Styrene-maleic acid copolymer (thickener) 50 mg / m ² Hardener (H-2) 10 mg / m ² (Backing layer coating solution) Gelatin 1.4 g / m ² compound (i) 80 mg / m ² compound (h) 15 mg / m ² compound (j) 150 mg / m ² saponin (20%) 0.6 ml / m ² latex (Lx -1) Synonymous with Example 1 300 mg / m ² 5-methylbenzotriazole 5 mg / m ² 5-nitroindazole 20 mg / m ² compound (d) 4 mg / m ² styrene-maleic acid copolymer (thickener) 50 mg / M ² Hardener H-1 10 mg / m ² (Backing protective layer coating solution) Gelatin 1.0 g / m ² Compound (i) 40 mg / m ² Compound (h) 100 mg / m ² Compound (j) 100 mg / m ² Surfactant S-3 (synonymous with Example 1) 5 mg / m ² spherical polymethylmethacrylate (4 μm) 25 mg / m ² Hardener Glioxa 10 mg / m ²

[0099]

[Chemical formula 23]

[0100]

[Chemical formula 24]

On the polyethylene terephthalate support having a thickness of 100 μm, each of the coating solutions prepared as described above was undercoated, a backing layer and a backing protective layer were applied in this order from the side closer to the support as the backing surface side. And dried. Then, an emulsion layer and an emulsion protective layer were applied in this order from the side closer to the support to the side opposite to the backing surface side of the support and dried.

The obtained sample was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0103]

[Table 2]

From the results shown in Table 2, the samples of the present invention showed good results for each item as in the case of the examples.

[0105]

The silver halide light-sensitive material according to the present invention comprises
Excellent resistance to blackening pressure due to scratches without degrading sensitivity.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material containing a hydrazine derivative in at least one silver halide emulsion layer and / or other hydrophilic colloid layer on a support, said silver halide emulsion layer and / or other Halogen containing a nucleation accelerator in the hydrophilic colloid layer and gelatin-stabilized polymer latex in the silver halide emulsion layer and / or other hydrophilic colloid layer. Silver halide photographic light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion comprises silver halide containing 50 mol% or more of silver chloride.