JP2805012B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an Ar (argon) laser which can be handled under a yellow safety light or a red safety light. The present invention relates to a silver halide photographic material which can be used as a silver halide photographic material for a scanner.

[Background of the Invention]

In recent years, the development of silver halide photographic light-sensitive materials has been remarkable. For example, in the technical field of photographic materials for plate making, as the plate making process becomes lighter, the light room (under a white fluorescent light or under a yellow safety light) is used. Silver halide photographic light-sensitive materials that can be handled have been widely used.

Against this background, the use of a color scanner with an Ar (argon) laser light source, which was conventionally handled under a red safety light in the plate making process, has required a bright room with a yellow safety light.

The output wavelength of the Ar laser light source is 488 nm. Therefore A
r As photosensitive material for laser light source scanners, 488
In order to make a photosensitive material that has photosensitivity in the nm section, can be handled under yellow safety light, and can also be handled under conventional red safety light, it is usually sensitive to wavelengths shorter than 540 nm. In general, spectral sensitization is performed so as to have

On the other hand, a color scanner is an apparatus that performs both color separation and halftone separation of a color original and prints the photosensitive material with a laser beam, and is currently generally used for producing printed matter from a color original.

This type of color scanner generally employs a drum type in which a photosensitive material is wound around a rotating drum and printed with a laser beam while rotating the drum.

However, if foreign matter such as dust adheres to the photosensitive material at the time of baking, floating occurs at the time of winding,
The phenomenon that the portion is black and blurred, or the image is out of focus, so-called "burning blur" occurs, hindering the plate-making operation, and improvement has been strongly desired.

[Problems to be solved by the invention]

Therefore, an object of the present invention is to handle under a yellow safety light safely, and furthermore, to safely handle under a conventional red safety light, and have a high sensitivity to an Ar laser light source with less occurrence of burning blur. The object of the present invention is to provide a silver halide photographic light-sensitive material having:

[Means for solving the problem]

As a result of intensive studies, the present inventors have found that, in a silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side on a support, at least one of the silver halide photographic materials is preferably used. In one layer, at least one compound selected from the compounds represented by the following general formula [I]
And a conductive layer between the photosensitive silver halide emulsion layer and the support and / or on the opposite side of the support with respect to the emulsion layer, the conductive layer comprising:
Water-soluble conductive polymer, hydrophobic polymer particles, and the reaction product of polyglycidol and epihalohydrin [C
A] or a silver halide photographic light-sensitive material characterized by containing a curing agent selected from the compounds represented by the following general formula [CB].

[In the formula, Z ¹ represents a nonmetallic atom group necessary to form a 5- to 6-membered heterocyclic ring, and Q represents a nonmetallic atomic group necessary to form a 5-membered nitrogen-containing heterocyclic ring. . R ¹ represents an alkyl group or a substituted alkyl group. m represents 1 or 2. ] In the formula, x, y, z, w represent an integer of 0 to 50, and R ₁ , R ₂ , R ₃ , R
₄ is a hydrogen atom, And R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. X represents a halogen atom, and R ₅ and R ₆ are a hydrogen atom or Represents

In addition, they have found that the object of the present invention can be more effectively achieved when the conductive layer contains a metal oxide.

 Hereinafter, the present invention will be described in detail.

First, the compound represented by the general formula [I] will be described.

In the general formula [I], Z ₁ is a group of non-metal atoms necessary for forming a 5- or 6-membered heterocyclic ring, and examples of the heterocyclic ring include a thiazole ring, a selenazole ring, an oxazole ring, and a benzoyl group. Thiazole ring, benzoselenazole ring, benzoxazole ring, naphthothiazole ring, naphthoselenazole ring, naphthoxazole ring, pyridine ring, quinoline ring, and the like, and further, these heterocycles may have a substituent. Often, these substituents include, for example, a halogen atom (eg, a chlorine atom, a bromine atom, etc.),
For example, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group), a halogenated alkyl group (for example, trifluoromethyl group or the like), an alkoxy group, preferably 1 carbon atom And alkoxy groups (e.g., methoxy group, ethoxy group, n-propyloxy group), hydroxy group, and aryl group (e.g., phenyl group).

Q represents a nonmetallic atom group necessary to form a 5-membered heterocyclic ring. Examples of the heterocyclic ring include a rhodanine ring, a thiohydantoin ring, a thiooxazolidinedione ring, a thioselenazolidinedione ring, and the like.These heterocyclic rings may have a substituent. Is preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, a 2-hydroxyethyl group, a 2-hydroxyethyloxyethyl group, a 2-methoxyethyl group, a 2-acetoxyethyl group Carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-
Sulfobutyl group, benzyl group, phenethyl group, n-butyl group, etc.), aryl group (eg, phenyl group, p-sulfophenyl group, etc.) or pyridyl group (eg, 2-pyridyl group, 3-pyridyl group, methyl-2-pyridyl) And the like).

R ₁ represents an alkyl group or a substituted alkyl group, for example, an alkyl group having 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl) , Hexyl, octyl, dodecyl, octadecyl and the like), substituted alkyl groups such as aralkyl groups (eg benzyl, 2-
Phenylethyl, etc.), hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl, etc.), carboxyalkyl group (eg, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl, etc.), alkoxyalkyl Groups (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl, etc.), sulfoalkyl groups (eg, 2
-Sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy]
Ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc., a sulfatoalkyl group (eg, 3-sulfatopropyl, 4-sulfatobutyl, etc.), a heterocyclic-substituted alkyl group (eg, 2-
(Pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl and the like), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl,
Examples include an allyl group. Next, specific examples of the compound represented by the general formula [I] used in the silver halide photographic light-sensitive material of the present invention are shown. However, needless to say, the compounds used in the present invention are not limited to these.

The compound represented by the above general formula [I] used in the present invention is described in U.S. Pat. No. 2,161,331 and West German Patent No. 93607.
It can be easily synthesized based on the method described in the specification of No. 1.

In order to use the compound represented by the general formula [I] in a silver halide emulsion, the compound is dissolved in a coating solution or dissolved in water or an organic solvent such as methanol, ethanol or acetone alone or a mixed solvent thereof. And may be added to the coating solution. However, if necessary, a silver halide emulsion layer can be added to an adjacent layer, for example, a protective layer or an intermediate layer, as long as the photographic performance is not affected.

The amount of the compound represented by the formula (I) contained in the silver halide photographic light-sensitive material of the present invention when added to a silver halide emulsion varies depending on the type of the silver halide emulsion and the type of the compound. However, the range is usually from 5 mg to 1000 mg per mol of silver halide.

In the present invention, typical methods for forming the conductive layer include a method using a water-soluble conductive polymer, hydrophobic polymer particles, a curing agent, and the like, and a method using a metal oxide.

As the water-soluble conductive polymer used in the former method,
Sulfonic acid group, sulfate group, quaternary ammonium salt,
Examples include polymers having at least one conductive group selected from tertiary ammonium salts and carboxyl groups.
The conductive groups require at least 5% by weight per polymer molecule. In the water-soluble conductive polymer, hydroxy group, amino group, epoxy group, aziridine group, active methylene group,
It may contain a sulfinic acid group, an aldehyde group and a vinyl sulfone group.

The molecular weight of the polymer is preferably from 3,000 to 100,000, more preferably from 3,500 to 50,000.

Hereinafter, examples of the compound of the water-soluble conductive polymer used in the present invention will be described, but the present invention is not limited thereto.

In the above A-1 to A-50, x, y, and z represent mol% of the monomer component, and n represents an average molecular weight (the average molecular weight indicates a number average molecular weight in the present specification).

These polymers can be synthesized by polymerizing a commercially available or conventional monomer.
The addition amount of these compounds is preferably from 0.01 to 10 g / m ^2, particularly preferably 0.1-5 g / m ^2.

These compounds can be used alone or in combination with various hydrophilic binders or hydrophobic binders to form a layer. Particularly useful as the hydrophilic binder are gelatin or polyacrylamide, but others include colloidal albumin, cellulose acetate, cellulose nitrate, polyvinyl alcohol, hydrolyzed polyvinyl acetate, phthalated gelatin. Can be Molecular weight 2 as hydrophobic binder
Styrene-butyl acrylate-acrylic acid terpolymer, butyl acrylate-acrylonitrile-acrylic acid terpolymer, methyl methacrylate-ethyl acrylate-acrylic acid terpolymer Is mentioned.

Hydrophobic polymer particles that can be contained in the conductive layer are composed of so-called latex particles that are substantially insoluble in water, and the hydrophobic polymer is not particularly limited, and styrene, a styrene derivative, an alkyl acrylate, an alkyl methacrylate, an olefin derivative, It can be obtained by polymerizing a monomer selected in any combination from halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile and the like.

In particular, the styrene derivative, alkyl acrylate, and alkyl methacrylate preferably contain at least 30 mol%, and particularly preferably 50 mol% or more.

Emulsion polymerization (emulsion polymerization method) is used to make the hydrophobic polymer into a latex state. The solid polymer is dissolved in a low-boiling-point solvent, finely dispersed, and then the solvent is distilled off (dispersion method).
There are two methods, all of which can be adopted. However, emulsion polymerization is preferred in that a fine particle having a uniform particle size can be obtained.

The molecular weight of the hydrophobic polymer may be 3000 or more, and there is almost no difference in transparency due to the molecular weight.

Hereinafter, specific examples of the hydrophobic polymer will be described, but the invention is not limited thereto.

 Specific examples of the hydrophobic polymer of the present invention will be described.

The addition amount of the hydrophobic polymer is preferably 0.01 to 10 g / m ^2,
Particularly preferably, it is 0.1 to 5 g / m ² .

As the activator used in the emulsion polymerization or the dispersant used in the dispersion method, a nonionic activator is used, and a polyalkylene oxide compound is preferably used.

The polyalkylene oxide compound refers to a compound containing a polyalkylene oxide chain of at least 3 or more and at most 500 or less in a molecule, for example, a polyalkylene oxide and an aliphatic alcohol, a phenol, a fatty acid,
Aliphatic mercaptans, condensation reaction with a compound having an active hydrogen atom such as an organic amine, or polypropylene glycol, a polyol such as a polyoxytetramethylene polymer to condense an aliphatic mercaptan, an organic amine, ethylene oxide, propylene oxide, etc. Can be synthesized.

The polyalkylene oxide compound may be a block copolymer in which the polyalkylene oxide chain in the molecule is divided into two or more instead of one.

At this time, the total polymerization degree of the polyalkylene oxide is 3
The number is preferably 100 or less.

Specific examples of the polyalkylene oxide compound optionally used in the invention are shown below.

As a curing agent that can be used for the conductive layer, there is a reaction product [CA] of polyglycidol and epihalohydrin. This is considered to be a mixture in terms of the synthesis method.However, since the effect of the present invention can be obtained by suppressing the number of hydroxy groups and the number of epoxy groups, it is not important whether or not the mixture is a mixture. It may be an isolate or a mixture.

Specific examples include, but are not limited to, the following.

Examples of the curing agent that can be used in the conductive layer include a compound represented by the following general formula [CB].

In the formula, x, y, z, w represent an integer of 0 to 50, and R ₁ , R ₂ , R ₃ , R
₄ is a hydrogen atom, And R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. X represents a halogen atom, and R ₅ and R ₆ are a hydrogen atom or Represents

Specific examples of the compound represented by the general formula [CB] are shown below, but it should not be construed that the invention is limited thereto.

The above compound may be dissolved in an organic solvent such as water or alcohol, acetone, or added as it is, or may be added after dispersing using a surfactant such as dodecylbenzene sulfonate or nonylphenoxyalkylene oxide. Is also good.

The preferable addition amount of the compounds represented by the general formulas [CA] and [CB] is preferably 1 to 1000 mg / m ² .

Next, a method for forming a conductive layer using a metal oxide will be described.

Preferred as the metal oxide are crystalline metal oxide particles, but those containing oxygen vacancies and those containing a small amount of heteroatoms forming donors for the metal oxide used are generally referred to as Particularly preferred because of its high conductivity,
In particular, the latter containing a small amount of heteroatoms forming a donor with respect to the metal oxide used is particularly preferable because it does not give fog to the silver halide emulsion.

Examples of metal oxides are ZnO ₂ , TiO ₂ , SnO ₂ , Al
₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O _{5 and the} like, or composite oxides thereof are preferable, and ZnO ₂ , TiO ₂ and SnO ₂ are particularly preferable.

As an example containing a hetero atom, for example, addition of Sb or the like to SnO ₂ or addition of Nb or Ta to TiO ₂ is effective. The addition amount of these different atoms is preferably in the range of 0.01 to 30 mol%, and particularly preferably in the range of 0.1 to 10 mol%.

The metal oxide particles used in the present invention have conductivity, and have a volume resistivity of 10 ⁷ Ωcm or less, particularly 1 Ωcm or less.
It is preferably at most 0 ⁵ Ωcm.

This oxide is disclosed in JP-A-56-143431 and JP-A-56-12.
Nos. 0519 and 58-626647.

The metal oxide particles are used by being dispersed or dissolved in a binder. The binder that can be used is not particularly limited as long as it has a film-forming ability.Examples include gelatin, proteins such as casein, carboxymethylcellulose, hydroxyethylcellulose, acetylcellulose, diacetylcellulose, and triacetylcellulose, dextran, and agar. , Sodium alginate, sugars such as starch derivatives, polyvinyl alcohol,
Polyvinyl acetate, polyacrylate, polymethacrylate, polystyrene, polyacrylamide,
Examples thereof include synthetic polymers such as poly-N-vinylpyrrolidone, polyester, polyvinyl chloride, and polyacrylic acid.

Especially gelatin (lime-processed gelatin, acid-processed gelatin,
Enzyme-degraded gelatin, phthalated gelatin, acetylated gelatin, etc.), acetylcellulose, diacetylcellulose, triacetylcellulose, polyvinyl alcohol,
Polyvinyl acetate, polybutyl acrylate, polyacrylamide, dextran are preferred.

To lower the resistance of the conductive layer by using the metal oxide more effectively, the volume content of the metal oxide in the conductive layer is preferably higher, but in order to have sufficient strength as a layer. Therefore, the volume percentage of the metal oxide is preferably in the range of 5 to 95%.

The amount of metal oxide is preferably 0.05 to 10 g / m ^2, more preferably 0.01-5 g / m ^2. Thereby, an antistatic property is obtained.

In the present invention, the conductive layer is provided between the silver halide emulsion layer and the support and / or on the opposite side of the support with respect to the emulsion layer. That is, it may be provided on the photosensitive emulsion side of the transparent support, or may be provided on the opposite side of the transparent support with respect to the photosensitive emulsion surface, that is, on the so-called back surface.

Such a conductive layer is formed on a transparent support by coating.

The transparent support can be any photographic one, but is preferably polyethylene terephthalate or cellulose triacetate made to transmit at least 90% of visible light.

These transparent supports are prepared by a method well known to those skilled in the art, but in some cases, even if a slight amount of a dye is added so as not to substantially impede light transmission and bluing is performed. good.

The support may be provided with an undercoat layer containing a latex polymer after the corona discharge treatment. In the corona discharge treatment, an energy value of 1 mW to 1 KW / m ² min is particularly preferably applied. It is particularly preferable to perform the corona discharge treatment again after the application of the latex subbing layer and before the application of the conductive layer.

At least one support is provided on the support having the conductive layer.
A light-sensitive silver halide emulsion layer is provided.

In the present invention, the photosensitive silver halide emulsion layer preferably contains a hydrazine compound, and examples of the hydrazine compound include compounds represented by the following general formula [H].

In the formula, R ₁ represents a monovalent organic residue, R ² represents a hydrogen atom or a monovalent organic residue, and Q ₁ and Q ₂ represent a hydrogen atom or an alkylsulfonyl group (including those having a substituent) ), An arylsulfonyl group (including those having a substituent), and X ₁ represents an oxygen atom or a sulfur atom. Among the compounds represented by the general formula [H], X ₁ is an oxygen atom,
Further, a compound in which R ₂ is a hydrogen atom is more preferred.

The monovalent organic residue of R ₁ and R ₂ includes an aromatic residue, a heterocyclic residue and an aliphatic residue.

Examples of the aromatic residue include a phenyl group, a naphthyl group and a substituent thereof (an alkyl group, an alkoxy group, an acylhydrazino group, a dialkylamino group, an alkoxycarbonyl group, a cyano group, a carboxy group, a nitro group, an alkylthio group, a hydroxy group, Sulfonyl group, carbamoyl group,
Halogen atom, acylamino group, sulfonamide group, urea group, thiourea group, etc.). Specific examples of those having a substituent include, for example, 4-methylphenyl group, 4-ethylphenyl group, 4-oxyethylphenyl group, 4-dodecylphenyl group, 4-carboxyphenyl group, 4-diethylaminophenyl group, -Octylaminophenyl group, 4-benzylaminophenyl group,
4-acetamido-2-methylphenyl group, 4- (3-
Ethylthioureido) phenyl group, 4- [2- (2,4-
Di-tert-butylphenoxy) butylamido] phenyl group, 1,1-dibenzylsemicarbazide group and the like.

The heterocyclic residue is a 5- or 6-membered monocyclic or condensed ring having at least one of oxygen, nitrogen, sulfur and selenium atoms, which may have a substituent. Specifically, for example, a pyrroline ring, a pyridine ring, a quinoline ring, an indole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, an imidazole ring, a benzimidazole ring, a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, Residues such as a selenazole ring, a benzoselenazole ring and a naphthoselenazole ring can be exemplified.

These heterocycles have 1 to 1 carbon atoms such as methyl group and ethyl group.
An alkyl group having 4 carbon atoms such as a methoxy group and an ethoxy group;
And an aryl group having 6 to 18 carbon atoms such as an alkoxy group or a phenyl group, a halogen atom such as chloro or bromo, an alkoxycarbonyl group, a cyano group or an amino group.

As the aliphatic residue, a linear or branched alkyl group,
Cycloalkyl groups and those having a substituent,
And alkenyl and alkynyl groups.

The linear or branched alkyl group is, for example, an alkyl group having 1 to 18, preferably 1 to 8 carbon atoms, and specifically, for example, a methyl group, an ethyl group, an isobutyl group,
Octyl group and the like.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, and specific examples include a cyclopropyl group, a cyclohexyl group, and an adamantyl group. Examples of the substituent for the alkyl group or the cycloalkyl group include an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an alkoxycarbonyl group, a carbamoyl group, a hydroxy group, an alkylthio group, an amide group, an acyloxy group,
Cyano group, sulfonyl group, halogen atom (for example, chlorine,
Bromine, fluorine, iodine, etc.), aryl groups (for example, phenyl group, halogen-substituted phenyl group, alkyl-substituted phenyl group) and the like. Specific examples of the substituted ones are, for example, 3-methoxypropyl group, ethoxycarbonylmethyl group, -Chlorocyclohexyl, benzyl, p-methylbenzyl, p-chlorobenzyl and the like. Examples of the alkenyl group include an allyl group, and examples of the alkynyl group include a propargyl group.

 Preferred specific examples of the hydrazine compound are shown below.

The hydrazine compound represented by the general formula [H] may be added to the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer on the side of the silver halide emulsion layer on the support. The silver halide emulsion layer and / or the lower layer thereof.

The addition amount is preferably from 10 ^-5 to 10 ^-1 mol / mol of silver, and more preferably from 10 ^-4 to 10 ^-2 mol / mol of silver.

In the present invention, the photosensitive silver halide emulsion layer preferably contains a tetrazolium compound.

Examples of the tetrazolium compound include compounds represented by the following general formula [T].

The substituents R ₁ , R ₂ , and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T] are hydrogen atoms or Hammett's sigma values (σ
P) is preferably negative or positive, and particularly preferably negative.

Hammett's sigma values for phenyl substitution are described in many publications, for example, Journal of Medical Chemistry 20, 304, 197.
For example, a group having a negative sigma value, such as a methyl group (σP = −0.17, both of which can be seen in a report by C. Hansch et al.
Value), ethyl group (-0.15), cyclopropyl group (-0.2
1), n-propyl group (-0.13), isopropyl group (-0.
15), cyclobutyl group (-0.15), n-butyl group (-0.
16), iso-butyl group (-0.20), n-bentyl group (-
0.15), a cyclohexyl group (-0.22), an amino group (-0.
66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27), ethoxy group (-0.07).
24), propoxy group (-0.25), butoxy group (-0.3
2), a pentoxy group (-0.34) and the like, all of which are useful as substituents of the compound of the general formula [T] of the present invention.

Hereinafter, specific examples of the compound of the general formula [T] used in the present invention will be shown, but the present invention is not limited thereto.

The tetrazolium compound can be easily synthesized, for example, according to the method described in Chemical Reviews, Vol. 55, pp. 335-483.

The tetrazolium compound is preferably used in a range of about 1 mg to 10 g per mol of silver halide contained in the silver halide photographic light-sensitive material, and more preferably in a range of about 10 mg to about 2 g. preferable.

In the present invention, a matting agent is preferably contained in the outermost layer on the side including or excluding the photosensitive silver halide emulsion layer.

Any known matting agent can be used. For example, silica described in Swiss patent 330,158, glass powder described in French patent 1,296,995, British patent
Inorganic particles such as alkaline earth metals or cadmium according to 1,173,181, carbonates such as zinc, U.S. Pat.
2,037, a starch derivative described in Belgian Patent 625,451 or British Patent 981,198, JP-B-44
Polyvinyl alcohol described in -3643, Swiss Patent 330,
Organic particles such as polystyrene or polymethyl methacrylate described in US Pat. No. 158, polyacrylonitrile described in US Pat. No. 3,079,257, and polycarbonate described in US Pat. No. 3,022,169 can be included.

These matting agents may be used alone or in combination. The shape of the matting agent is preferably spherical as a regular matting agent, but may be other shapes such as a flat plate or a cubic shape.

The size of the matting agent is preferably in the range of 0.1 to 10 μm, more preferably in the range of 2 to 8 μm. Here, the average particle size means a diameter obtained by converting the diameter of a spherical agent into a spherical volume if the particle is a non-spherical particle, and converting the volume of the matting agent into a spherical volume if the particle is other than a spherical particle.

Also, the fact that the matting agent is contained in the outermost layer means that at least a part of the matting agent may be contained in the outermost layer, and a part of the matting agent may reach a layer below the outermost layer. .

Further, in order to fulfill the basic function of the matting agent, it is desirable that a part of the matting agent is exposed on the surface. In addition, the matting agent exposed on the surface may be a part or all of the added matting agent. The method for adding the matting agent may be a method in which the matting agent is dispersed in the coating solution in advance, or a method in which the matting agent is sprayed before the drying is completed after the coating solution is applied. Good. When a plurality of different matting agents are added, both methods may be used in combination.

The silver halide emulsion may be any silver halide emulsion such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. The silver halide grains can be used and may be obtained by any of an acidic method, a neutral method, and an ammonia method.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. Particles formed on the surface or particles formed mainly inside the particles may be used.

The silver halide emulsion used in the present invention is, for example, U.S. Pat.Nos. 2,444,607, 2,716,062 and 3,512,982
No. 1,189,380, West German Application Publication No. 2,058,626,
Nos. 2,118,411, JP-B-47-4417, West German Application Publication No. 2,149,789, JP-B-39-2825, JP-B-49-13566, etc. , 6-Trimethylene-7-hydroxy-S-
Triazolo (1,5-a) pyrimidine, 5-methyl-7-
Hydroxy-S-triazolo (1,5-a) pyrimidine,
7-hydroxy-S-triazolo (1,5-a) pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-triazolo (1,5-a) pyrimidine, isoamyl gallate, dodecyl gallate, gallic acid Propyl, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-nitro Benzimidazole) or the like.

In the present invention, the photosensitive material and / or the developer may contain an amino compound.

Further, in order to enhance the developability, a developing agent such as phenidone or hydroquinone and an inhibitor such as benzotriazole can be contained in the emulsion side. Alternatively, in order to increase the processing ability of the processing solution, the backing layer may contain a developing agent or an inhibitor.

A particularly preferred hydrophilic colloid for the present invention is gelatin. The gelatin used in the present invention may be either alkali-treated or acid-treated, but when ossein gelatin is used, it is preferable to remove calcium or iron. The calcium content is preferably 1 to 999 ppm, more preferably 1 to 500 ppm.
And the iron content is preferably from 0.01 to 50 ppm, more preferably from 0.1 to 10 ppm. Such a method of adjusting the amounts of calcium and iron can be achieved by passing an aqueous gelatin solution through an ion exchange device.

As a developing agent used for developing the photosensitive material, catechol, pyrogallol and its derivatives and ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2,3-dibromohydroquinone, 2,5-diethylhydroquinone, 4-chlorocatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, sodium ascorbate and the like.

Ortho and para aminophenols are typical HO- (CH = CH) _a -NH ₂ type developers.
4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, N-methyl-p-aminophenol and the like.

Further, examples of the H ₂ N- (CH ＝ CH) _a -NH ₂ type developer include 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N- (4
-Amino-3-methylphenyl) -morpholine, p-phenylenediamine and the like.

Examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. -Pyrazolidones,
Examples thereof include 1-phenyl-4-amino-5-pyrazolone and 5-aminolausyl.

TH The James, The Theory of Photograh Process 4th Edition (The Theory of Photogra
phic Process Fourth Edition) pp. 291-334 and Journal of the American Chemical Society, 73.
Vol. 3, page 100 (1951).

These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination.
Further, even when a sulfite is used as a preservative in the developer, the effect of the present invention is not impaired. In addition, hydroxylamine and hydrazide compounds can be used as preservatives. In this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g per developer.

Further, the developer may contain glycols as an organic solvent. Examples of such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, and 1,5-pentanediol. However, diethylene glycol is preferably used. The amount of these glycols used is preferably from 5 to 500 g, more preferably from 20 to 200 g, per developer. These organic solvents can be used alone or in combination of two or more.

The pH value of the developer is preferably from 9 to 13, but the pH value is more preferably from 10 to 12 from the viewpoint of preservation and photographic characteristics. As for the cations in the developer, it is preferable that the ratio of potassium ions to sodium is higher because the activity of the developer can be increased.

The light-sensitive material according to the present invention can be processed under various conditions. The processing temperature is, for example, preferably a development temperature of 50 ° C. or lower, particularly preferably around 25 ° C. to 40 ° C., and the development time is generally completed within 2 minutes, particularly preferably 10 seconds to 50 seconds. In many cases, it is effective. Processing steps other than development, such as washing, stopping, stabilizing, fixing,
Further, if necessary, it is optional to adopt steps such as prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these processes may be so-called hand developing processes such as plate developing and frame developing, or may be mechanical developing such as roller developing and hanger developing.

The present invention can be applied to all photosensitive materials in which at least one photosensitive silver halide emulsion layer is formed on a support. For example, a color photosensitive material, an X-ray photosensitive material, a printing plate-making photosensitive material, and the like can be used.

〔Example〕

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

Example 1 (Preparation of Support Having Conductive Layer) After corona discharge on a 100 μm-thick subbed polyethylene terephthalate support, a liquid having the following composition was
It was applied at a speed of 70 m / min using a roll-fit coating pan and an air knife so that the following amount was obtained.

Water-soluble conductive polymer A (Table 1) 0.6 g / m ² hydrophobic polymer particles B (Table 1) 0.2 g / m ² polyethylene oxide compound (molecular weight 500) 0.06 g / m
² Curing agent C (Table 1) 0.2 g / m ² This was dried at 90 ° C. for 2 minutes and heat-treated at 140 ° C. for 90 seconds. The conductive layer coated on one side and both sides of the support was prepared as shown in Table 1.

(Preparation of the coating solution for the emulsion layer and the protective layer above the emulsion layer) Solution A water 9.7 sodium chloride 20 g gelatin 105 g solution B water 3.8 sodium chloride 94 g gelatin 365 g potassium bromide 450 g 0.01% aqueous solution of potassium hexachloroiridate
28 ml 0.01% aqueous solution of potassium hexabromorhodate 1.
0 ml Solution C Water 3.8 Silver nitrate 1700 g To the above solution A kept at 40 ° C., while simultaneously maintaining pH 3 and pAg 7.7, simultaneously add the above solution B and solution C functionally over a period of 60 minutes, and then continue for 10 minutes. PH was adjusted to 6.0 with sodium carbonate aqueous solution, 20% magnesium sulfate aqueous solution 2 and 5% aqueous solution of polynaphthalenesulfonic acid
Add 2.55, flocculate the emulsion at 40 ° C, decant and wash with water to remove excess aqueous salts. Then add water of 3.7 and disperse it again
0.9% of a 0% aqueous solution of magnesium sulfate is added in the same manner to remove excess salts of the aqueous solution. Add 3.7 g of water and 141 g of gelatin thereto and disperse at 55 ° C. for 30 minutes. Thus, silver bromide 32 mol%, silver chloride 68 mol%, average particle size 0.25 μm,
An emulsion having a monodispersity of 9 is obtained.

2600 ml of this emulsion was weighed, and 40 ml of a 1% aqueous solution of citric acid and 100 ml of an aqueous solution of 5% potassium bromide were added to adjust the pH and pAg. The emulsion thus obtained is added with 20 ml of a 0.1% aqueous solution of sodium thiosulfate and 30 ml of a 0.1% aqueous solution of chloroauric acid, and ripened at 60 ° C. for about 3 hours to obtain the highest sensitivity.

1-phenyl-5 was added to the above emulsion as an antifoggant.
25 ml of a 0.5% solution of mercaptotetrazole, 600 ml of a 1% solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and 690 ml of a 10% aqueous solution of gelatin were added, followed by aging. Stopped. To this emulsion, the above-mentioned general formula [I] was added so as to give a coating amount of 4 mg / m ² as shown in Table 1, and 20% of hydroquinone was used as an antifoggant.
70% solution, 60% aqueous saponin solution as spreading agent 60
ml, 4% of styrene-maleic acid polymer as thickener
130 ml of an aqueous solution and 84 g of a polymer latex of ethyl acrylate were added and stirred, and citric acid 1 was added.
The pH and pAg were adjusted by adding 35 ml of a 5% aqueous solution and 60 ml of a 5% aqueous solution of potassium bromide.

The coating solution for the protective layer was prepared as follows. That is, 105 ml of a 10% aqueous solution of potassium bromide was added to an aqueous solution containing 600 g of gelatin, and 1-decyl-2- (3
375 ml of a 1% aqueous solution of -isopentyl) succinate-2-sulfonate. Compound II described below was added to the liquid thus obtained at a concentration of 45 mg / m ² and stirred.

(Preparation of Coating Solution for Back Layer and Protective Layer Above Back Layer) A water-soluble dye compound described below is added to an aqueous solution containing 700 g of gelatin.
2960 ml of a 2% aqueous solution of III-1 and 62% of a 2% aqueous solution of III-2
0 ml and 499 ml of a 5% aqueous solution of the same III-3 were added. Further, 825 ml of a 0.75% methanol solution of 5-nitroindazole as an inhibitor, 210 ml of a 20% aqueous saponin solution as a spreading agent, 200 ml of a 4% aqueous solution of a styrene-maleic acid polymer as a thickener, butyl acrylate 105 g of high polymer latex was added.
50% aqueous solution was added and stirred. Thus, a coating solution for forming the back surface layer was prepared.

Further, as a coating solution for forming a protective layer on the back layer,
To an aqueous solution containing 600 g of gelatin, 4.48 g of polymethyl methacrylate having an average particle size of about 0.4 μm and 360 ml of a 10% aqueous solution of sodium chloride were added as a matting agent, and 1-decyl-2- (3-in) was used as a spreading agent. Pentyl) succinate-2-sodium sulfonate 1% aqueous solution (500 ml) was added,
Stirred.

(Preparation of Sample) Of the coating solutions for the emulsion layer, the protective layer above the emulsion layer, the back layer, and the protective layer above the back layer, the coating solution for the protective layer above the emulsion layer was prepared as described above. An aqueous solution of sodium salt of formalin and 2,4-dichloro-6-hydroxytriazine and an aqueous solution of bisvinylsulfonylmethyl ether are added as a hardening agent, and glyoxazole and bisvinylsulfonylmethyl ether as a hardening agent are added to the coating solution for the back layer. Glyoxal and bisvinylsulfonylmethyl ether as a hardening agent were added to the coating solution for the protective layer on the upper surface of the back layer, and then 30 W / m ² was applied to one side of the support.
・ After corona discharge with energy of min- ¹ , the emulsion layer is coated simultaneously so that the silver amount is 4.25 g / m ² , and the protective layer is further overlaid on top so that the gelatin amount is 1.36 g / m ^2. did.
And on the side opposite to the emulsion layer, after corona discharge at an energy of 30W / m ² · min ^-1, the back surface layer, gelatin amount, 2.26
g / m ² , and a protective layer was simultaneously applied thereon so that the amount of gelatin became 1.34 g / m ² .

(Development processing conditions) The formulas of the used developer and fixer are shown below.

<Developer formulation> Pure water (ion-exchanged water) Approx. 300 ml Potassium nitrite 60 g Disodium ethylenediaminetetraacetate 2 g Potassium hydroxide 10.5 g 5-methylbenzotriazole 300 mg Diethylene glycol 25 g 1-phenyl-4,4-dimethyl-3-pyrazolidone 300
mg 1-phenyl-5-mercaptotetrazole 6 mg Potassium bromide 3.5 g Hydroquinone 20 g Potassium carbonate 15 g Add pure water (ion-exchanged water) to make 1,000 ml.

 The pH of this developer was about 10.8.

<Composition A> (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240ml Sodium nitrite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% W / W aqueous solution) ) 13.6 ml (composition B) pure water (ion-exchanged water) 17 ml sulfuric acid (50% W / W aqueous solution) 4.7 g when using aluminum sulfate (Al ₂ O ₃ in terms of content of 8.1% W / W aqueous solution) 26.5 g fixer The above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 for use.

 The pH of the fixing solution was about 4.3.

 The automatic processor used was Konica GR-27.

 The developing conditions are shown below.

Developing 28 ° C 30 seconds Fixing 28 ° C 20 seconds Washing 20 ° C 14 seconds Draining 20 ° C 6 seconds Drying 50 ° C 28 seconds The sample (shown in Table 1) obtained at ambient temperature 23
After conditioning for 2 hours under the condition of ℃, environment relative humidity 20%,
The following baking blur forced deterioration test was performed. Table 1 shows the results.

(Bake-Bokeh Forced Deterioration Test) The sample conditioned as described above was forcibly charged with a rubber roller at an ambient temperature of 23 ° C. and a relative humidity of 20% to bring the film surface into contact with the tobacco ash. Then, after lightly brushing the attached tobacco ash with a brush, the film was washed with an Ar laser scanner SG-80 manufactured by Dainippon Screen Mfg. Co., Ltd.
The film was wound around an 8II drum, and a halftone dot image was wound around the drum, and then processed with an automatic processor. The degree of occurrence of blurring in the obtained image was evaluated based on the following criteria.

：: No occurrence Δ: Occurrence is recognized, but the degree is very small and there is no problem in practical use ×: Not practical As is evident from Table 1, the samples of Nos. 2 to 8 of the present invention are preferable because they are free from burning blurring and are preferable.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the tetrazolium compound T-2 was added to the emulsion coating solution.

 As a result, a result equivalent to that of Example 1 was obtained.

Example 3 The same experiment as in Example 2 was performed, except that the hydrazine compound (H-47) was used in place of the tetrazolium compound T-2 used in Example 2.

Example 4 (Preparation of Support Having Conductive Layer) After corona discharge was performed on a 100 μm-thick subbed polyethylene terephthalate support, a conductive layer having the following structure was applied.

This was dried at 90 ° C. for 2 minutes and heat-treated at 140 ° C. for 90 seconds. This conductive layer was prepared by coating the support on only one side and both sides.

A sample was prepared in exactly the same manner as in Example 1 except that an emulsion layer, an emulsion protective layer, a back surface layer, and a back surface protective layer were provided. However, a hydrazine compound (H-47) was added to the emulsion layer. Using the obtained sample, a forced baking blur deterioration test was performed.

As a result, it was found that the sample of the present invention provided with the above-mentioned conductive layer did not suffer from blurring and produced good results, as compared with the sample not provided with the conductive layer.

〔The invention's effect〕

As is apparent from the above description, according to the present invention, handling under a yellow safety light is safe, and further, handling under a conventional red safety light is safe, and an Ar laser with less burning blur is obtained. A silver halide photographic light-sensitive material having high sensitivity to a light source can be provided.

Continuation of the front page (56) References JP-A-62-291636 (JP, A) JP-A-1-274131 (JP, A) JP-A-61-174542 (JP, A) JP-A-58-58541 (JP) JP-A-60-254042 (JP, A) JP-A-57-104931 (JP, A) JP-A-57-118242 (JP, A) JP-A-60-23848 (JP, A) (58) Surveyed field (Int.Cl. ⁶ , DB name) G03C 1/76 G03C 1/08

Claims (2)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side of a support, wherein at least one layer of the silver halide photographic material has the following general formula: It contains at least one compound selected from the compounds represented by the formula [I], and has a conductive material in the middle of the photosensitive silver halide emulsion layer and the support and / or on the opposite side of the support with respect to the emulsion layer. A cured layer selected from a water-soluble conductive polymer, hydrophobic polymer particles, and a reaction product of polyglycidol and epihalohydrin [CA] or a compound represented by the following general formula [CB]. Silver halide photographic material characterized by containing an agent. [Wherein, Z ¹ represents a non-metallic atom group necessary for forming a 5- to 6-membered heterocyclic ring, and Q represents a non-metallic atomic group necessary for forming a 5-membered nitrogen-containing heterocyclic ring. . R ¹ represents an alkyl group or a substituted alkyl group. m represents 1 or 2. ] In the formula, x, y, z, w represent an integer of 0 to 50, and R ₁ , R ₂ , R ₃ , R ₄
Is a hydrogen atom, And R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. X represents a halogen atom, and R ₅ and R ₆ are a hydrogen atom or Represents 2. The silver halide photographic light-sensitive material according to claim 1, wherein the conductive layer contains a metal oxide.