JPH07319110A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material improved in resistance to pressure marks by using a hydrazine derivative or a pyridinium salt derivative as a nucleator. CONSTITUTION:(1) The photosensitive material having at least one silver halide emulsion layer and at least one protective layer above the emulsion laver has a ratio of protective layer hardness to emulsion layer hardness each measured by a thin film hardness meter of <0.95; (2) the photosensitive material contains a polymer having a glass transition point of <=40 deg.C in an amount of >=0.1g/m<2> in the protective layer and a solid filler in an amount of >=0.1g/m<2> in the emulsion layer; and (3) the photosensitive material contains at least one of the hydrazine derivative and the pyridiniumm salt derivative as the nucleator.

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 having improved pressure fog, and more particularly to a silver halide photographic light-sensitive material which prevents scratch-like fog generated during transportation and handling of the light-sensitive material.

[0002]

2. Description of the Related Art It is known that a silver halide photographic light-sensitive material causes pressure fog when it is brought into contact with various devices during a manufacturing process or during handling such as exposure and development.

As a method for improving the pressure fog, many proposals have already been made. For example, in Japanese Patent Laid-Open No. 4-214551,
A method of using colloidal silica for the emulsion layer and a sliding agent for the protective layer, or JP-A-4-337723 discloses a method of making the swelling rate of the film in water above a certain level.

However, with the rapid development process, pressure fog is likely to occur due to high-speed transport of the film and reduction of the binder of the photosensitive material. In particular, when a nucleating agent such as a hydrazine derivative or a pyridinium salt derivative is used as a contrast-increasing agent in a light-sensitive material for printing, scratch-like pressure fog is more likely to occur during rapid processing, and its solution has been desired.

As is well known, the hydrazine derivative contains 0.15 mol / liter or more of sulfite ion when incorporated into a surface latent image type silver halide photographic light-sensitive material as described in US Pat. Nos. 4,224,401 and 4,269,929. p
It has been proposed as a system capable of obtaining a super-high contrast negative image having a γ (gamma) of more than 10 by processing with a developing solution having a storage stability of H11.0 to 12.3 having a relatively good storage stability.

However, in such a developing system, p of the developing solution is
Since H was relatively high at 11.0 to 12.3, it was easily affected by air oxidation and the storability of the developer was not sufficient. Therefore pH1
A method has been proposed in which a highly active hydrazine derivative that causes a high contrast even in a developing solution of 1.0 or less and a compound that promotes a nucleation reaction (nucleation accelerator) are added to a light-sensitive material. As the highly active hydrazine derivative, for example, European Patent 333,435, U.S. Patents 4,988,604, 4,994,346, JP-A-63-234244.
And JP-A-63-249838.

Examples of the nucleation accelerator include JP-A-60-14034.
No. 0, 63-124045, 63-133145, U.S. Patent 4,975,3
54 and 4,963,956.

However, by promoting the nucleation reaction by the highly active hydrazine derivative and the nucleation accelerator, the nucleation action is remarkably promoted and the contrast of the photosensitive material for printing is increased, but as described above, the pressure fog is generated. Increasing number of times, high than before
It has been found that the fog resistance is significantly deteriorated as compared with the pH system.

As a nucleating agent other than the hydrazine derivative, a method using a pyridinium salt derivative disclosed in, for example, JP-A Nos. 1-217339 and 5-53231 is known, and also in this image forming system. The same phenomenon as in the case of using a hydrazine derivative was observed, and improvement in pressure fog resistance was desired.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material in which pressure fog is prevented, especially for printing using a hydrazine derivative or a pyridinium salt derivative as a nucleating agent. It is to improve the scratch-like pressure fog of the light-sensitive material.

[0011]

The above objects of the present invention are as follows.
The present invention has been solved by the following.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and at least one protective layer above the emulsion layer, the protective layer measured by a thin film hardness meter A silver halide photographic light-sensitive material, characterized in that the ratio of the hardness to the hardness of the silver halide emulsion layer is less than 0.95.

(2) 0.1 g of a polymer having Tg of 40 ° C. or less is contained in the protective layer.
g / m ² or more, and 0.1 g / m of solid filler in the emulsion layer
^The silver halide photographic light-sensitive material according to the item (1), which contains ^two or more.

(3) The silver halide photographic light-sensitive material according to item (1) or (2), which contains at least one of a hydrazine derivative and a pyridinium salt derivative as a nucleating agent.

The present invention will be described in detail below.

The hardness measured by the thin film hardness meter referred to in the present invention means, specifically, the thin film hardness meter MHA-400 (manufactured by NEC Corporation).
Was used as a parameter of the pushing load and the pushing speed at that time.

Although the hardness of the thin film changes depending on the environmental humidity, the value of the present invention is a value measured in an environment at 23 ° C. and 50% relative humidity.

The hardness of each of the protective layer and the emulsion layer was determined as follows.

Protective layer: Determined as the hardness when an indenter was pressed to a thickness of 50% of the thickness of the protective layer observed by SEM using a photosensitive material containing a support as a sample.

Emulsion layer: The thickness of the emulsion layer observed by SEM using a sample with the protective layer peeled off using a microtome.
It was calculated as the hardness when the indenter was pushed in to a thickness of 50%.

When there are two or more emulsion layers, the hardness of the emulsion layers contributing to image formation is indicated. When there are two or more layers contributing to image formation, a microtome is used for the upper layers up to each layer. Was peeled off, the hardness of each layer was measured, and the value of the layer with the lowest hardness was used.

When there are two or more protective layers above the emulsion layer, the hardness of each layer was measured to obtain the value of the layer having the lowest hardness. The hardness ratio between the protective layer and the silver halide emulsion layer is calculated by the following formula.

Hardness [GPa] of protective layer / Hardness [GPa] of emulsion layer In the present invention, the above ratio is less than 0.95, preferably 0.85 or less, and more preferably 0.8 or less.

As a means for increasing the hardness of the emulsion layer, a method of adding a solid filler can be mentioned. As a solid filler, JP-A-55-126239, colloidal silica described in JP-A-4-214551, colloidal montmorillonite clay described in JP-A-60-202438 or phosphate represented by hydroxyapatite, smectite. Typical examples include tabular silica, inorganic substances such as zeolite, and polymer particles having a Tg of 40 ° C. or higher. These solid fillers are preferably surface-treated for the purpose of stabilizing dispersion. As a specific example of the surface treatment, for example, JP-A-4-25
A coat of a silane coupling agent or a coat of a titanium coupling agent as described in No. 7849 is preferably used.

The solid filler will be described in detail.

Colloidal Silica The colloidal silica used in the present invention (colloidal silica) has an average particle size of 0.005 to 1.0 μm, preferably 0.005 to 0.
At 5 μm, the main component is silicon dioxide, and it may contain alumina, sodium aluminate or the like as a minor component. Further, these colloidal silica may contain an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia as a stabilizer. For these colloidal silica, for example, JP-A-53-112732,
It is disclosed in Japanese Patent Publication Nos. 57-9051 and 57-51653.

Specific examples of the colloidal silica include Snowtex 30 (SiO ₂ / Na ₂ O ≧ 57), Snowtex C (SiO ₂ / Na ₂ O ≧ 100), Snowtex O (S
iO ₂ / Na ₂ O ≧ 500), or Ludox AM, etc. are commercially available.

Here, SiO ₂ / Na ₂ O means silicon dioxide (SiO 2
₂ ) and the content weight ratio of sodium hydroxide are expressed by converting sodium hydroxide to Na ₂ O, and all are the values described in the catalog.

Tabular silica The tabular silica used in the present invention means a layered silicate containing alkali, alkaline earth metal, aluminum and the like, and examples thereof include kaolin mineral, mica clay mineral and smectite. Kaolin minerals include kaolinite, decite, nacrite, halloysite, and serpentine. Examples of mica clay minerals include pyrophyllite, talc, muscovite, swellable synthetic fluoromica, sericite, and chlorite. As smectite, smectite,
Examples thereof include vermiculite and swellable synthetic fluorine vermiculite.

Among these, two types are preferable, natural products and synthetic products. Examples of natural products are montmorillonite and beidellite, which are obtained as clays called acid clay and are used as antistatic agents. Examples of use in the photosensitive hydrophilic colloid layer is, for example, JP-A-60-202438,
No. 60-239747. However, synthetic compounds are most preferably used because of their excellent transparency, and there are also those containing fluorine for the purpose of improving heat resistance. Specific examples of the synthetic smectite include, for example, Lucentite SWN and SWF of Cope Chemical Co., Ltd. These tabular silicas are preferably tabular silicas having an aspect ratio of 2 or more in 50% of the total projected area of all silicas in the emulsion layer used.

The aspect ratio mentioned here represents the ratio of the diameter of a circle having the same area as the projected area of the flat silica and the distance between two parallel planes. In the present invention, the aspect ratio is preferably 2 or more and less than 100, particularly preferably 2 or more and less than 50. The tabular silica of the present invention has a thickness of 1.0 μm or less, preferably 0.5 μm or less.

The tabular grain distribution is 30% or less in terms of the coefficient of variation (100 times the value S / D obtained by dividing the standard deviation S when the projected area is approximated to a circle by the diameter D), which is often used. A monodisperse content of 20% or less is preferable, but it is not an essential requirement.

Phosphate The phosphate used in the present invention means an inorganic compound having phosphoric acid as a constituent element and a complex of the inorganic compound and an organic compound. Examples of the phosphate include apatite, naconone, ammonium phosphate, calcium phosphate, cobalt phosphate, zirconium phosphate, sodium phosphate, magnesium phosphate, silver phosphate and the like. Among them, apatite is preferably used. What is apatite M ₁₀ (ZO
₄ ) A compound belonging to the hexagonal system with a basic composition of ₆ X ₂ . There are various combinations of M, Z, and X in the formula, but it is possible to substitute various elements having a valence of 1 to 3 for M, a valence of 3 to 7 for Z, and a valence of 0 to 3 for X.

In many cases, holes are partially formed in M or X. Specifically, hydroxyapatite Ca ₁₀ (PO ₄ ) ₆
(OH) ₂ , fluoroapatite Ca ₁₀ (PO ₄ ) ₆ F ₂ , chlorine apatite Ca ₁₀ (PO ₄ ) ₆ (OH) _2, and the like. The apatite may be dense, porous, or a composite structure thereof, and may have any of a spherical shape, an amorphous shape, a needle shape, and a flaky shape. These apatites are, for example, K. Hirota et al., Yogyo-Kyokaishi, 90,680 (1982), H. Monm.
In addition, it can be synthesized with reference to J. Chem. Tech. Biotechnol. 31, 15 (1981) and the like.

Zeolites Zeolites used in the present invention are aluminum silicates, and based on Al ₂ O ₃ , XM ₂ /nO.Al ₂ O ₃ .yS.
It has a basic composition of iO ₂ · ZH ₂ O. It has a three-dimensional network structure in which SiO ₄ and AlO ₄ tetrahedra share vertices. M represents an ion-exchangeable metal ion (for example, Na, K, Ca, Ba, etc.), and n represents a valence. X and y represent the coefficient of metal oxide and silica, and Z represents the number of crystal water.

There are natural and synthetic zeolites, and any of them can be used. However, synthetic zeolites are preferably used because they contain few impurities. Examples of natural zeolites include analsite, erionite, modelite, chavanite, gmelinite, and levinite. Examples of the synthetic zeolite include zeolite A, zeolite X, zeolite Y, zeolite L, and synthetic mordenite.

The zeolite may have any of spherical, amorphous, acicular and flaky shapes. The synthetic zeolite can be synthesized, for example, by the method described in JP-A-56-155941.

Examples of commercially available products include 3A manufactured by Tosoh Corporation,
4A, 5A, AW-500, 10X, 13X, Molecular Sieve LINDER ZB-300 manufactured by Union Carbite Co., silicalite, ZSM-5 manufactured by Mobil Co., and the like.

The particle size of the solid filler is preferably as small as possible because it is directly added to the emulsion layer, and preferably 1 μm or less,
It is particularly preferably 0.1 μm or less. Addition amount is 0.1g / m
² or more, more preferably 0.2 g / m ² or more 1.0
g / m ² or less.

In the present invention, various plasticizers can be used as a means for lowering the hardness of the protective layer. Specific examples of the plasticizer in the present invention, Tg is a polymer of 40 ℃ or less, alkyl phthalate described in British Patent 738,637,
Alkyl esters described in U.S. Pat. No. 738,689, U.S. Patent 2,960,4
Examples of polyhydric alcohols described in No. 04, preferably
It is a polymer with Tg of 35 ° C or less. The form of the polymer as the plasticizer in the present invention may be either water-insoluble or water-soluble, and the form of water-insoluble polymer latex is particularly preferable. Examples of the polymer latex contained in the protective layer of the present invention include US Pat.
2,166, 3,325,286, 3,411,911, 3,311,912
Nos. 3,525,620, Research Disclosure 19551 (July 1980) and the like, which are hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters, and styrene.

Preferred polymer latexes having a Tg of 40 ° C. or lower are homopolymers of alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, or alkyl acrylate and acrylic acid,
Copolymer with N-methylol acrylamide, etc. (preferably the copolymerization component with acrylic acid etc. is up to 30% by weight),
Examples thereof include a homopolymer of butadiene, a copolymer of butadiene and styrene, butoxymethyl acrylamide, one or more of acrylic acid, and a vinylidene chloride-methyl acrylate acrylic acid terpolymer.

The Tg of the polymer latex can be determined by the method of differential scanning calorimetry (DSC). The average particle size of the polymer latex used in the present invention is 0.005 to 1
μm, especially 0.02 to 0.3 μm. The amount of polymer latex added is 5 per weight of hydrophilic colloid in the layer to be added.
~ 200%, especially 10-100% is preferred.

Specific examples of the polymer latex are shown below.

[0044]

[Chemical 1]

In addition to the above, JP-A-6-43572 and JP-A-6-6572
Polymer latexes described in 0-31135 and 59-224839 can be preferably used.

A hydrazine derivative or a pyridinium salt derivative is used as a nucleating agent in the light-sensitive material of the present invention.

The hydrazine derivative used in the present invention is
It can be represented by the following general formula [H].

[0048]

[Chemical 2]

In the formula, A ₀ represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples include, for example, methyl, ethyl, t-butyl, octyl, cyclohexyl, benzyl group and the like, and these are further suitable substituents (for example, aryl, alkoxy, aryloxy,
(Alkylthio, arylthio, sulfoxy, sulfonamide, sulfamoyl, acylamino, ureido groups, etc.)
May be replaced with.

The aromatic group represented by A ₀ 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 ₀ is preferably a monocycle or a condensed ring containing at least one hetero atom selected from nitrogen, sulfur and oxygen atoms, and examples thereof include pyrrolidine, imidazole, tetrahydrofuran, morpholine and pyridine. Pyrimidine, quinoline,
Examples thereof include thiazole, benzothiazole, thiophene and furan ring. Particularly preferred as A ₀ are an aryl group and a heterocyclic group. The aromatic group and heterocyclic group of A ₀ may have a substituent. Particularly preferred groups include a substituent having an acidic group having a pKa of 7 or more and 11 or less, and specific examples thereof include a sulfonamide group, a hydroxyl group, and a mercapto group.

A ₀ 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 is a photographically inactive group having 8 or more carbon atoms, such as an alkyl group, an alkenyl group or an alkynyl group, Alkoxy group, phenyl group,
Examples thereof include a phenoxy group and an alkylphenoxy group.

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 ₀ represents a blocking group, preferably a -G ₀ -D ₀ group.

G ₀ is a --CO-- group, a --COCO-- group, a --CS-- group,
_{-C (= NG 1 D 1)} - group, -SO- group, -SO ₂ - group or -P (O)
Represents a (G ₁ D ₁ )-group. G ₁ is a simple bond, -O- group, -S-
Represents a group or a -N (D ₁ )-group. D ₁ is an aliphatic group, an aromatic group,
When a plurality of D _1's are present in the molecule and represent a heterocyclic group or a hydrogen atom, they may be the same or different.

D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group. Preferable G ₀ is —CO— group, and —COCO— group, and particularly preferably —COCO—
Groups. Preferred D ₀ includes a hydrogen atom, an alkoxy group, an amino group and the like.

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 (ethoxalyl, etc.). Etc.).

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

[0058]

[Chemical 3]

[0059]

[Chemical 4]

[0060]

[Chemical 5]

[0061]

[Chemical 6]

[0062]

[Chemical 7]

Next, the pyridinium salt derivative used in the present invention is represented by the following general formula [Pa], [Pb] or [Pc].

[0064]

[Chemical 8]

In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a non-metal atom group for completing the nitrogen-containing heterocycle,
It may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴
And the heterocycle composed of A ⁵ may have a substituent, and they may be the same or different. As the substituent, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an aryloxy group. , Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group,
It represents a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, or an arylthio group. Preferred examples include A ¹ , A ² , A ³ , A ⁴ and A ^{5 which} are 5- or 6-membered rings (for example, pyridine, imidazole, thiozole, oxazole, pyrazine, pyrimidine rings, etc.). A pyridine ring can be mentioned.

B _P represents a divalent linking group, and the divalent linking group is alkylene, arylene, alkenylene, --SO _2- ,
-SO -, - O -, - S -, - CO -, - N (R 6) -, represents what is configured alone or in combination (R ⁶ is an alkyl group, an aryl group, a hydrogen atom) . As a preferred example, B
Examples of _p include alkylene, alkenylene, and alkylene oxide.

R ¹ , R ² and R ⁵ represent a saturated or unsaturated alkyl group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different. As the substituents, A ¹ , A ² ,
It has the same meaning as the groups mentioned as the substituents for A ³ , A ⁴ and A ⁵ .

As a preferred example, R ¹ , R ² and R ⁵ each represent an alkyl group having 4 to 10 carbon atoms. Further preferable examples are a substituted or unsubstituted aryl group and a substituted alkyl group. X _p represents a counter ion required to balance the charge of the entire molecule, and represents, for example, chloride ion, bromine ion, iodide ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an intramolecular salt. Specific compound examples are shown below.

[0069]

[Chemical 9]

[0070]

[Chemical 10]

[0071]

[Chemical 11]

[0072]

[Chemical 12]

[0073]

[Chemical 13]

In the present invention, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb] in order to effectively accelerate the contrast increase by the hydrazine and pyridinium compounds.

[0075]

[Chemical 14]

In the general formula [Na], R ₁₁ , R ₁₂ , and R ₁₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. A ring can be formed by R ₁₁ , R ₁₂ , and R ₁₃ . 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 particularly preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific examples of these nucleation accelerator general formula [Na] compounds are given below.

[0078]

[Chemical 15]

[0079]

[Chemical 16]

[0080]

[Chemical 17]

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group, but Ar and R ₁₄ may be connected by a connecting group to form a ring. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Further, as a preferable silver halide adsorbing group, a group having the same meaning as the silver halide adsorbing group of the compound represented by the general formula [H] can be mentioned.

Specific examples of the compound of the general formula [Nb] include those shown below.

[0083]

[Chemical 18]

[0084]

[Chemical 19]

In the present invention, the effect of the present invention was great when a nucleation accelerator having a molecular weight of 500 or less was used. The hydrazine derivative or pyridinium salt derivative and the nucleation accelerator used in the present invention may be used in any layer on the silver halide emulsion layer side, preferably in the silver halide emulsion layer or its adjacent layer. Is preferred.

The optimum addition amount is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the kind of the inhibitor, etc., but generally 10 mol per mol of silver halide is used. ^-6 mol to 10 ^-1 mol range is preferred, especially 10
A range of ^-5 mol to 10 ^-2 mol is preferred.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited in halogen composition, but is preferably silver chloride, silver chlorobromide or silver chloroiodobromide. The average grain size of the silver halide grains is preferably 0.7 μm or less, and particularly preferably 0.5 μm to 0.1 μm.
The average particle diameter as used herein means the particle diameter when the particles are spherical or can approximate a sphere. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size.
See CEK Mees & T. For details on how to determine the average particle size.
By H. James. The theory of the photographic process.
The third edition, pages 36 to 43 (1966. Published by Macmillan) can be referred to.

The shape of silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape or the like may be used. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable. As a method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

For the silver halide emulsion, a method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in the liquid phase where silver halide is formed, that is, a controlled double jet method can be used. A silver halide emulsion having a substantially uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, or at least one of them during the grain forming process or the growing process. It is preferable to add a complex salt containing the element.

For the silver halide emulsion and its preparation method, see Research Disclosure (RD) 17643.22-23 (1978.
You can refer to the method described in (December).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used in addition to the sulfur compounds contained in gelatin.

The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound, ascorbic acid and the like can be used.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7 -Tetrazaindenes), pentazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added.

The silver halide emulsion layer and the protective layer according to the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-
Hydroxy-s-triazine, etc.), mucohalogenates (mucochloric acid, phenoxymucochloric acid, etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc. may be used alone or in combination. it can.

The photosensitive emulsion layer, protective layer and other non-photosensitive hydrophilic colloid layers according to the present invention have improved coating properties, antistatic properties, slipperiness, emulsion dispersibility, anti-adhesion properties and photographic properties. For the purpose of, various surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

The light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (eg vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination,
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

The silver halide emulsion is preferably spectrally sensitized with various spectral sensitizing dyes. Preferred sensitizing dyes include (RD) 17643.23 to 24 (December 1978) and (R
D) 34685 (1993) can be used.

Various other additives are used in the light-sensitive material according to the present invention. For example, desensitizer, plasticizer, slip agent,
Development accelerators, oils, dyes, etc. These are (RD) 17643.23
The materials described on page 31 can be used.

The emulsion layer and the protective layer of the light-sensitive material according to the present invention may each be a single layer or a multilayer composed of two or more layers. In the case of multiple layers, an intermediate layer or the like may be provided between them.

The emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Useful as the flexible support are films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene and polyethylene terephthalate.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (eg 1-phenyl-3
-Pyrazolidone, 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diamino) Phenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1
-(p-Methylaminophenyl) -3-aminopyrazoline, 1- (p
-Aminophenyl) -3-aminopyrazoline, 1- (p-amino-N
-Methylphenyl) -3-aminopyrazoline etc.) can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes or It is preferable to use a combination of 3-pyrazolidones and ascorbic acid and a combination of aminophenols and ascorbic acid. The developing agent is usually 0.01 to 1.4
It is preferably used in an amount of mol / l.

As a silver sludge inhibitor, Japanese Patent Publication No. 62-4702
No. 3, JP-A-51844, No. 4-26838, No. 4-362942,
Examples thereof include the compounds described in 1-319031. Further, as sulfites and metabisulfites used as preservatives, sodium sulfite, potassium sulfite, ammonium sulfite,
For example, sodium metabisulfite. The sulfite is preferably 0.25 mol / liter or more. It is particularly preferably 0.4 mol / liter or more.

If necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) may be added to the developer. , Solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.),
Surfactants, antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerator (for example, US Pat. No. 2,304,025)
Nos. 4,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg, glutaraldehyde or its bisulfite adduct), or a defoaming agent. The pH of the developer is preferably adjusted to 9.5-10.5.

The light-sensitive material of the present invention is used as an activator processing solution containing a developing agent in a light-sensitive material, for example, an emulsion layer, as a special form of development processing, and processing the light-sensitive material in an alkaline aqueous solution to perform development. May be. Such a developing treatment is often used as one of the rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and can be applied to such a processing solution.

As the fixing solution for developing the light-sensitive material of the present invention, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used. A water-soluble aluminum salt that acts as a hardening agent, such as aluminum chloride, aluminum sulfate, and potassium alum, can be added to the fixing solution. If desired, the fixer may contain a compound such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent having a water softening ability. You can

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

The development temperature of the silver halide photographic light-sensitive material of the present invention can be set in the usual temperature range of 20 to 30 ° C. or in the high temperature processing range of 30 to 40 ° C. You can also

The silver halide photographic light-sensitive material of the present invention is preferably processed using an automatic processor. At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The developer replenishment amount is preferably 300 ml or less per 1 m ² in order to reduce the amount of waste liquid, and particularly preferably 75 to 200 ml per 1 m ² .

The development time is the total processing time (Dr from the time when the leading edge of the film is inserted into the automatic developing machine to the time when it comes out of the drying zone when processing using the automatic developing machine due to the demand for reduction.
y to Dry) is preferably 20 to 60 seconds. The total processing time referred to here includes all process times required for processing the black-and-white light-sensitive material, and specifically, for processing, for example, developing, fixing, bleaching, washing, stabilizing, drying, etc. It is the time that includes all the process time, that is, the time to Dry to Dry.
More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

[0113]

EXAMPLES The effects of the present invention will be specifically illustrated by the following examples.

Example 1 (Preparation of silver halide emulsion) 70 mol% of silver chloride, 30 of silver bromide
A silver nitrate aqueous solution and a mixed aqueous solution of NaCl and KBr were mixed by a controlled double jet method to grow a silver halide grain so as to have a mol% silver halide composition. At this time, the mixing was carried out under the conditions of 36 ° C., pAg 7.8 and pH 3.0, and 2 × 10 ⁻⁷ mol of Na ₃ RhCl ₆ was added per 1 mol of silver during grain formation. After the completion of mixing, 80 mg of the following S-1 was added per mol of silver. After that, desalting was carried out with a modified gelatin treated with phenyl isocyanate, and the following compounds [A] [B]
A bactericide consisting of the mixture of [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%. The emulsion thus obtained contains 4-hydroxy-6 per mole of silver.
-Methyl-1,3,3a, 7-tetrazaindene (60 mg) was added, and 5 mg chloroauric acid and 0.5 mg sulfur flower were added to 1 mol of silver, and the pH was adjusted to 5.8 and pAg 6.5 at 60 ° C, 80 ° C. Chemical aging was performed for a minute. After ripening, add 900 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per 1 mol of silver, and add KI300
mg, S-2 350 ml were added.

(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 2.6 g / m ^{2 and the} amount of silver was 3.3 g / m ²
And a protective layer of the following formulation (2) on it so that the amount of gelatin is 1.0 g / m ² .
On the other undercoat layer on the opposite side, a backing layer was applied according to the following prescription (3) so that the amount of gelatin would be 3.1 g / m ^2, and a protective layer of the following prescription (4) was further applied thereon. Was coated so that the amount of gelatin would be 1 g / m ² to obtain a sample.

Formulation (1) [Silver halide emulsion layer composition] Gelatin 2.6 g / m ² Silver halide emulsion Silver amount 3.3 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² : 5-nitroindazole 10 mg / m ² Nucleating agent: Compound of Table 1 3 × 10 ⁻⁵ mol / m ² Nucleating accelerator: Compound of Table 1 1 × 10 ⁻⁴ mol / m ² Polymer latex 1 1.6 g / m ² Solid filler Amount shown in Table 1 Colloidal silica 0.5 g / m ² Compound K 45 mg / m ² Water-soluble polymer V-1 20 mg / m ² Surfactant: saponin 0.1 g / m ² : sodium sulfosuccinate isopentyl normal decyl ester 8 mg / m ² Formulation (2) [Emulsion protective layer composition] Gelatin 1.0 g / m ² Plasticizer Amount described in Table 1 Matting agent: Silica having an average particle size of 3.5 μm 20 mg / m ² Surfactant: Sodium sulfosuccinate di (2 -Ethylhexyl) ester 10 mg / m ² Surfactant F-1 2 mg / m ² Accelerator: High Doloquinone 50mg / m ² : 1-phenyl-4-hydroxymethyl-4'-methyl-3-pyrazolidone 5mg / m ² Hardener: Formalin 30mg / m ²

[0117]

[Chemical 20]

[0118]

[Chemical 21]

Formulation (3) [Backing layer composition]

[0120]

[Chemical formula 22]

Gelatin 3.1 g / m ² Surfactant: sodium dodecylbenzenesulfonate 50 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / m ² colloidal silica 0.5 g / m ² Formula (4) [backing protective layer composition ] Gelatin 1 g / m ² Matting agent: Polymethylmethacrylate having an average particle size of 4.0 μm 50 mg / m ² Surfactant: Sodium sulfosuccinate: Di (2-ethylhexyl) ester 10 mg / m ² Hardener: -Formalin 12 mg / m ² 2-Hydroxy-4,6-dichloro-1,3,5-triazine 120 mg / m ^{2 The} obtained sample was evaluated by the following method.

Evaluation of Sample (Sensitivity and Gamma) The obtained sample was brought into close contact with a step wedge, exposed to a tungsten light of 3200 ° K for 3 seconds, and developed and fixed to determine the sensitivity. The sensitivity is the 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 at transmission densities of 1.0 to 3.0. Gamma needs to be 10 or more for practical use.

(Measurement of Thin Film Hardness) Measuring instrument: thin film hardness meter MHA-400 manufactured by NEC Corporation Measuring conditions: 23 ° C. 50% relative humidity Measuring method: The measuring method was performed as described above.

(Evaluation of Scratches [Scratch-like Fogging]) The obtained sample was put on a 10 × 10 cm acrylic plate in an environment of 23 ° C. and RH of 50% with a double-sided tape so that the backing layer side was face-up. A load of 500 g was applied. Then, the backing layer side and the emulsion layer side of the obtained sample were rubbed together.

After that, development processing was carried out by the same method as that for obtaining the sensitivity, and scratches (scratch fog) were visually evaluated in the following 5 grades.

1: Strong scratches were generated on the entire surface 2: Strong scratches were generated on a part. There is a problem in practical use 3: There is some weak scratches but there is no problem in practical use 4: Some extremely weak scratches occur 5: No occurrence (processing conditions) Developer formulation Sodium sulfite 50g 1- Phenyl-4-methyl, 4'-hydroxymethyl-3-pyrazolidone 0.85mg Diethylenetriamine pentaacetic acid 1.5g Boric acid 8g Potassium bromide 4g Potassium carbonate 55g 5-Methylbenztriazole 200mg Hydroquinone 20g Potassium hydroxide pH 10.4 When using Water was added to make 1 liter.

Fixer formulation 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 aqueous solution) 15.7 g Gluconic acid (50% w / w aqueous solution) 8.55 g Aluminum sulphate (48% aqueous solution) 13 ml Glutaraldehyde 3 g Sulfuric acid Amount to bring the pH to 4.6 when used. Water was added to make 1 liter.

(Development processing conditions) (Process) (Temperature) (Time) Current image 35 ° C 30 seconds Settling 33 ° C 20 seconds Water washing 15 minutes normal temperature Drying 40 ° C 15 seconds or more Shown in the table below.

[0129]

[Table 1]

[0130]

[Table 2]

As is apparent from the table, the sample according to the present invention shows less scratch fog on the film without deteriorating the sensitivity and gamma.

[0132]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material in which pressure fog is prevented without degrading sensitivity and gamma even in a light-sensitive material using a hydrazine derivative or a pyridinium salt derivative as a nucleating agent. I was able to.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and at least one protective layer above the emulsion layer, and the hardness of the protective layer measured by a thin film hardness meter. And a hardness ratio of the silver halide emulsion layer is less than 0.95, a silver halide photographic light-sensitive material. 2. A polymer having a Tg of 40 ° C. or less is 0.1% in the protective layer.
g / m ² or more, and 0.1 g / m of solid filler in the emulsion layer
^{2. The} silver halide photographic light-sensitive material according to claim 1, containing ^two or more. 3. The silver halide photographic light-sensitive material according to claim 1, which contains at least one of a hydrazine derivative and a pyridinium salt derivative as a nucleating agent.