JP2829635B2 - Silver halide photographic material with antistatic treatment - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an antistatic layer for a plastic film support, and more particularly to a silver halide photographic material having excellent antistatic ability.

[Background of the Invention]

In general, a plastic film support has a strong chargeability, and in many cases, this has imposed many restrictions on use. For example, a support such as polyethylene terephthalate is generally used in a silver halide photographic light-sensitive material, but is easily charged particularly at low humidity such as in winter. In recent years, when a high-sensitivity photographic emulsion is coated at a high speed, or when a high-sensitivity photosensitive material is exposed through an automatic printer, antistatic measures are particularly important.

When the photosensitive material is charged, the discharge produces a static mark or adheres foreign matter such as dust, thereby causing pinholes and significantly deteriorating the quality.
Because of the correction, workability is greatly reduced. For this reason, photosensitive materials generally use an antistatic agent, and recently, a fluorinated surfactant, a cationic surfactant, an amphoteric surfactant, a surfactant or polymer containing a polyethylene oxide group, a sulfonic acid or Polymers having a phosphate group in the molecule are used.

In particular, charge train adjustment with a fluorine-based surfactant or improvement in conductivity with a conductive polymer has been frequently used. For example, JP-A-49-91165 and JP-A-49-121523 disclose a dissociative group in the polymer main chain. An example in which an ionic polymer having the following formula is applied is disclosed.

However, in these conventional techniques, the antistatic ability is greatly deteriorated by the development processing. This is presumably because the antistatic ability is lost due to the steps of developing with an alkali, fixing with an acid, washing with water, and the like.
Therefore, when printing is further performed using a processed film, such as a printing photosensitive material, a problem such as generation of pinholes due to adhesion of dust occurs. Therefore, for example, JP-A-55-84658 and JP-A-61-174542 propose an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine. According to this method, the antistatic ability can be left after the treatment, but the transparency is still insufficient.

Further, it was found that when a super-high-contrast emulsion using a tetrazolium compound or a hydrazine compound was applied to the plastic film support having the antistatic layer, there was a problem that the sensitivity was reduced with the lapse of time.

[Object of the invention]

In view of the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having a haze-free antistatic layer excellent in transparency, and yet another object is to provide a tetrazolium compound or a hydrazine compound. An object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in antistatic ability even when used and has high stability without desensitization over time.

[Constitution of the Invention] The object of the present invention is to provide a photosensitive emulsion layer on a plastic film support having an antistatic layer comprising a reaction product of a water-soluble conductive polymer, hydrophobic polymer particles, and a curing agent. In the silver halide photographic light-sensitive material having, the hydrophobic polymer particles are styrene and a carbon
Characterized in that the photosensitive emulsion layer comprises a tetrazolium compound or a hydrazine compound, and is dispersed and stabilized by a nonionic surfactant having an alkylene oxide chain of 3 or more. And a silver halide photographic light-sensitive material.

 Hereinafter, details of the present invention will be described.

The water-soluble conductive polymer of the present invention can form a transparent layer even when used alone, but causes cracking of the layer due to slight fluctuation of drying conditions. In the structure of the present invention, hydrophobic polymer particles are contained to prevent the cracks, but the effect is large.

The water-soluble conductive polymer according to claim 1 of the present invention contains at least one conductive group selected from a sulfonic acid group, a sulfate ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, and a polyethylene oxide group. Having a polymer. Among these groups, a sulfonic acid group, a sulfate group, and a quaternary ammonium base are preferable. The conductive groups require at least 5% by weight per polymer molecule. Of the carboxy, hydroxy, amino, epoxy, aziridine, active methylene, sulfinic, aldehyde, and vinyl sulfone groups contained in the water-soluble conductive polymer, carboxy, hydroxy, and amino groups , An epoxy group, an aziridine group and an aldehyde group are preferred. These groups require 5% by weight or more per polymer molecule. The molecular weight of the polymer is 3000
1100,000, preferably 3500 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 (1) to (50), x, y, and z each represent mol% of a monomer component or an average molecular weight (in the present specification, the average molecular weight indicates a number average molecular weight). .

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

Next, the hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are contained in a so-called latex state which is substantially insoluble in water. This hydrophobic polymer is
It is obtained by polymerizing a monomer selected from styrene, a styrene derivative, an alkyl acrylate, and an alkyl methacrylate in any combination. In particular, it is preferable that at least 10 mol% of a styrene derivative, an alkyl acrylate, or an alkyl ruthacrylate is contained. Especially
30 mol% or more is preferable.

There are two methods to make a hydrophobic polymer into latex by emulsion polymerization, or by dissolving a solid polymer in a low boiling point solvent and finely dispersing it, and then distilling off the solvent, but the particle size is small and uniform. Emulsion polymerization is preferred from the viewpoint that a product can be obtained.

As the surfactant used in the emulsion polymerization, it is preferable to use a nonionic surfactant, and in the present invention, those having an alkylene oxide chain n = 3 or more described later are used. It is preferably 10% by weight or less based on the monomer. A large amount of surfactant causes the conductive layer to become cloudy.

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.

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

In the present invention, a conductive layer is provided on a transparent support. The transparent support may 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 of the present invention may be provided with an undercoat layer containing a latex polymer after the corona discharge treatment.
Corona discharge treatment is performed at an energy value of 1 mW / 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.

As the compound for curing the conductive layer of the present invention, a polyfunctional aziridine is preferable. In particular, bifunctional and trifunctional compounds having a molecular weight of 600 or less are preferable.

The conductive layer of the present invention may be on the support side of the photosensitive layer, or may be on the opposite side of the support with respect to the photosensitive layer, that is, on the back side.

A nonionic activator is used as the dispersant of the present invention,
Polyalkylene oxide compounds are preferably used.

The polyalkylene oxide compound used in the present invention refers to at least 3 or more, at most 500
Refers to a compound containing a polyalkylene oxide chain below, for example, a polyalkylene oxide and a fatty alcohol, a phenol, a fatty acid, an aliphatic mercaptan, by a condensation reaction with a compound having an active hydrogen atom such as an organic amine, or polypropylene glycol, It can be synthesized by condensing an aliphatic mercaptan, an organic amine, ethylene oxide, propylene oxide, or the like with a polyol such as a polyoxytetramethylene polymer.

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.

The hydrazine compound used in the present invention is preferably a compound represented by the following general formula [H].

In the formula, R ₁ represents a monovalent organic residue, ₂ represents a hydrogen atom or a monovalent organic residue, and Q ₁ and Q ₂ represent a hydrogen atom, an alkylsulfonyl group (including those having a substituent) Represents an arylsulfonyl group (including those having a substituent);
X ₁ represents an oxygen atom or a sulfur atom. Among the compounds represented by the general formula [H], compounds wherein X ₁ is an oxygen atom and R ₂ is a hydrogen atom are 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 (for example, 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 , A sulfonyl group, a carbamoyl group, a halogen atom, an acylamino group, a sulfonamide group, a urea group, a 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, 4
-Octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2-methylphenyl group, 4
-(3-ethylthioureido) phenyl group, 4- [2-
(2,4-di-tert-butylphenoxy) butyramide]
Examples include a phenyl group and a 4- [2- (2,4-di-tet-butylphenoxy) butylamido] phenyl group.

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.

Aliphatic residues include straight-chain and branched alkyl groups, cycloalkyl groups and those having a substituent, alkenyl groups and alkynyl groups.

Examples of the linear or branched alkyl group include those having 1 carbon atom
To 18 and preferably 1 to 8 alkyl groups, specifically, for example, methyl group, ethyl group, isobutyl group, 1-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 (eg, phenyl group, halogen-substituted phenyl group, alkyl-substituted phenyl group) and the like. Specific examples of the substituted ones include, 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 of the present invention are shown below, but the present invention is not limited thereto.

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

Next, the tetrazolium compound used in the present invention will be described.

The tetrazolium compound can be represented by the following general formula.

In the present invention, the substituent R ₁ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₂ and R ₃ are preferably a hydrogen atom or a compound having a Hammett sigma value (σP) indicating a degree of electron withdrawing property of negative or positive. Particularly, a negative one is preferable.

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 preferable negative sigma value is, for example, a methyl group ([sigma] P = -0.17 or less, all of which have a negative sigma value).
P 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-pentyl 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 are shown, but the compound of the present invention is not limited thereto.

The tetrazolium compound used in the present invention is described, for example, in Chemical Reviews, Vol. 55, No. 33.
It can be easily synthesized according to the method described on pages 5 to 483.

The tetrazolium compound of the present invention is preferably used in an amount of about 1 mg to 10 g, more preferably about 10 mg to about 2 g, per 1 mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention.

The silver halide emulsion used in the light-sensitive material of the present invention may be a silver halide emulsion such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or silver chloroiodobromide. Any used silver halide grains can be used.
Any of the acidic method, neutral method and ammonia method may be used.

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. The particles may be particles formed mainly within the particles or particles formed mainly inside the particles.

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,
No. 2,118,411, Japanese Patent Publication No. 43-4133, U.S. Pat.
2,596, JP-B-47-4417, West German Application Publication No. 2,149,7
No. 89, JP-B-39-2825, JP-B-49-13566, etc., and compounds described in each specification or gazette, preferably, for example, 5,6-trimethylene-7-hydroxyne-S-triazolo (1. , 5-a) pyrimidine, 5,6-tetramethylene-
7-hydroxy-S-triazolo (1,5-a) pyrimidine, 5-methyl-7-hydroxy-S-triazolo (1,5
5-a) Pyrimidine, 5-methyl-7-hydroxy-S
-Triazolo (1,5-a) pyrimidine, 7-hydroxyn-S-triazolone (1,5-a) pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-triazolo (1,5-a) Pyrimidine, gallic esters (eg, isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromo) Benztriazole, 5-methylbenztriazole), benzimidazoles (6-nitrobenzimidazole) and the like can be used.

The silver halide photographic light-sensitive material and / or the developer according to the present invention may contain an amino compound.

Further, in order to enhance 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. As a preferable content, the calcium content is 1 to 99.
9 ppm, more preferably 1 to 500 ppm, iron content is preferably 0.01 to 50 ppm, more preferably 0.1 to 10 ppm
It is. 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 silver halide photographic light-sensitive material according to the present invention, catechol, pyrogallol and its derivatives and ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone,
There are 2,3-dibromohydroquinone, 2,5-diethylhydroquinone, catechol, 4-chlorocatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, sodium ascorbate and the like.

Also, HO- as the (CH = CH) _n -NH ₂ type developer, the ortho and para aminophenols representative and 4-
Examples include aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, N-methyl-p-aminophenyl and the like.

Further, as an H ₂ N- (CH ＝ CH) _n -NH ₂ type developer, for example, 4-amino-2-methyl-N, N-diethylaniline,
There are 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.

The Theory of Photograph 4th Edition by TH James
ic Process Fourth Edition) pp. 291-334 and Journal of the American Chemical Society, 73.
Vol. 3, page 100 (1951), which can be effectively used in the present invention. These developers may be used alone or in combination of two or more.
It is preferable to use two or more kinds in combination. Further, even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material according to the present invention, the effects of the present invention are not impaired. 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.

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

The silver halide photographic light-sensitive material according to the present invention can be subjected to a developing treatment using a developer containing a development inhibitor as described above to obtain a light-sensitive material having extremely excellent storage stability.

The pH value of the developer having the above composition 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 silver halide photographic material according to the present invention can be processed under various conditions. As for the processing temperature, for example, the development temperature is preferably 50 ° C. or lower, particularly preferably about 25 ° C. to 40 ° C., and the development time is generally completed within 2 minutes, particularly preferably 10 seconds to 50 seconds. Often has a positive effect. Processing steps other than development, such as washing, stopping,
It is optional to employ steps such as stabilization and fixing, and if necessary, forehardening, neutralization, etc., and these steps may be omitted as appropriate. Further, these processes may be so-called hand developing processes such as plate developing and frame developing, or mechanical developing such as roller developing and hanger developing.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples. still,
As a matter of course, the present invention is not limited to the embodiments described below.

Reference Example 1 8 w / m ^{2 of} polyethylene terephthalate treated with undercoat
-After performing corona discharge with energy of min, an antistatic liquid having the following composition was applied using a roll-fit coating pan and an air knife at a speed of 30 m / min so as to give the following amount.

Water-soluble electroconductive polymer (A) 0.6 g / m ² hydrophobic polymer particles of the present invention (B) 0.4 g / m ² nonionic surfactant (Ao) 0.004g / m ² Note hydrophobic polymer particles (B), It was dispersed with a nonionic surfactant and used as a latex.

It was dried at 90 ° C. for 2 minutes and heat-treated at 140 ° C. for 90 seconds. Gelatin was applied on this antistatic layer so as to be 2.0 g / m ² , and a haze test was performed. Formalin and sodium 2,4-dichloro-6-hydroxy-S-triazine were used as hardeners for gelatin. The results are shown in Table 1.

(Haze test) The film support was measured using a turbidimeter Model T-2600DA manufactured by Tokyo Denshoku Co., Ltd., and the haze was indicated as a percentage.

The results in Table 1 show that the sample of the present invention is excellent in haze.

Example 1 (Preparation of emulsion) Rhodium salt containing 10 ^-5 mol per mol of silver, average grain size 0.11 μm, silver halide composition monodispersity by a controlled double jet method in an acidic atmosphere of pH 3.0. 15,
Silver chlorobromide particles containing 5 mol% of silver bromide were prepared. Particles were grown by adding benzyladenine to a 1% aqueous gelatin solution.
Per system. After mixing silver and halide, 600 mg of 6-methyl-4-hydroxy-1,3,3a, 7 tetrazaindene was added per mol of silver halide, and then washed with water and desalted.

Then, after adding 60 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene per mol of silver halide, 15 mg of sodium thiosulfate per mol of silver halide was added, and the mixture was added at 60 ° C. For sulfur sensitization. After sulfur sensitization, 600 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer per mole of silver halide.

Additives were added to the obtained emulsion so as to be in the following amounts, and coated on a latex-subtracted 100 μm-thick polyethylene terephthalate support according to Example 1 of JP-A-59-19941. .

Latex polymer: styrene - butyl acrylate - acrylic acid terpolymer polymer 1.0 g / m ² tetraphenylphosphonium chloride 30 mg / m ² Saponin 200 mg / m ² polyethylene glycol 100 mg / m ² hydroquinone 200 mg / m ² Styrene - maleic acid copolymerization 20 mg / m ² hydrazine compound (shown in Table 2) 50 mg / m ² 5-methylbenzotriazole 30 mg / m ² Desensitizing dye (M) 20 mg / m ² Alkali-treated gelatin (isoelectric point 4.9) 1.5 g / m ² bis (vinylsulfonylmethyl) ether 15 mg / m ² silver amount 2.8 g / m ² (Emulsion layer protective film) An emulsion layer protective film was prepared so as to have the following coating weight.
Co-layered with emulsion.

Fluorinated dioctyl sulfosuccinate 200 mg / m ² sodium dodecylbenzenesulfonate 100 mg / m ² Matting agent: polymethyl methacrylate (average particle size 3.5μ
m) 100 mg / m ² Lithium nitrate 30 mg / m ² Propyl gallate 300 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 30 mg / m ² Alkaline-treated gelatin (isoelectric point 4.9) 1.3 g / m ² Colloidal silica 30 mg / m ² Styrene-maleic acid copolymer 100 mg / m ² Bis (vinylsulfonylmethyl) ether 15 mg / m ² Then, 30 mg / m ^{2 was} previously placed on the support opposite to the emulsion layer.
After corona discharge at a power of W / m ² min, a poly (styrene-butyl acrylate-glycidyl methacrylate) latex polymer was applied in the presence of a hexamethylene-1,6-diaziridine hardener, and an antistatic layer was further implemented. Coating was performed in the same manner as in Example 1, and then a backing layer having the following composition was prepared and applied so that the additives would have the following amounts.

(Backing layer) Latex polymer: butyl acrylate-styrene copolymer 0.5 g / m ² styrene-maleic acid copolymer 100 mg / m ² citric acid (adjusted to pH 5.4 after coating) 40 mg / m ² saponin 200 mg / m ² Lithium nitrate 30mg / m ² Alkali-treated gelatin 2.0 g / m ² bis (vinylsulfonylmethyl) ether 15 mg / m ² (protective film for backing layer) An additive was prepared so as to have the following coating weight, and was simultaneously overlaid on the backing layer.

Dioctyl sulfosuccinate 200 mg / m ² Matting agent: polymethyl methacrylate (average particle size 4.0μ
m) 50 mg / m ² alkali-treated gelatin (isoelectric point 4.9) 1.0 g / m ² fluorinated sodium dodecylbenzenesulfonate 50 mg / m ² bis (vinylsulfonylmethyl) ether 20 mg / m ² The pH of the above coating solution Was prepared in advance to 5.4 and then applied.

The sample obtained as described above was divided into two, and one was stored at 23 ° C. and 55% relative humidity for 3 days. The other one was conditioned at 23 ° C. and a relative humidity of 55% for 3 hours, sealed in a moisture-proof bag in a stacked state, stored at 55 ° C. for 3 days, and forcibly degraded to prepare a sample for an age. Both samples were exposed through a step wedge and developed using the following developing solution and fixing solution, and then the sensitivity and surface resistivity were determined. Note that the sensitivity was an exposure amount at which the optical density was 1.0, and was expressed as a relative sensitivity. The results are shown in Table 2.

Processing conditions Process Temperature Time Development 34 ° C 15 seconds Fixing 32 ° C 10 seconds Rinse at room temperature 10 seconds Developer formulation Hydroquinone 25 g 1-Phenyl-4,4dimethyl-3-pyrazolidone 0.4 g Sodium bromide 3 g 5-Methylbenzotriazole 0.3 g 5-nitroindazole 0.05 g diethylaminopropane-1,2-diol 10 g potassium sulfite 90 g 5-sodium sulfosalicylate 75 g sodium ethylenediaminetetraacetate 2 g

 The pH was adjusted to 11.5 with caustic soda.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% aqueous solution) 240ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% aqueous solution) 13.6ml (Composition B) Pure Water (ion-exchanged water) 17 ml Sulfuric acid (50 w% aqueous solution) 4.7 g Aluminum sulfate (aqueous solution having an equivalent content of 8.1 w% in terms of Al ₂ O ₃ ) 26.5 g When using a fixing solution, the above composition A and composition B Melted in order and finished to 1 for use. The pH of the fixing solution was about 4.3.

From the results shown in Table 2, it can be seen that the sample of the present invention shows little decrease in sensitivity due to storage over time and little deterioration in antistatic ability after treatment.

Example 2 In the same manner as in Example 2, the rhodium salt was added per mole of silver.
Containing 10 ^-5 mol, was prepared an average particle size 0.20 [mu] m, silver bromide monodispersity 20 2 mol% comprising silver chlorobromide grains. This was desalted and sulfur sensitized in the same manner as in Example 2.

An additive was prepared and added to the obtained emulsion so as to have the following amount, and coated on the undercoated polyethylene terephthalate support used in Example 1.

Latex polymer: styrene-butyl acrylate acrylic acid terpolymer 1.0 g / m ² phenol 1 mg / m ² saponin 200 mg / m ² sodium dodecylbenzenesulfonate 50 mg / m ² tetrazolium compound (shown in Table 3) 50 mg / m ² Compound (N) 40 mg / m ² Compound (O) 50 mg / m ² Styrene / maleic acid copolymer 20 mg / m ² Alkaline treated gelatin (isoelectric point 4.9) 2.0 g / m ² Silver amount 3.5 g / m ² Formalin 10mg / m ² The coating solution was applied after adjusting to sodium hydroxide pH 6.5 in advance. As an emulsion protective film, an additive was prepared so as to have the following amount, and was simultaneously coated with an emulsion coating solution.

Fluorinated dioctyl sulfosuccinate 100 mg / m ² Dioctyl sulfosuccinate 100 mg / m ² Matting agent: amorphous silica 50 mg / m ² compound (O) 30 mg / m ² 5-methylbenzotriazole 20 mg / m ² compound (P) 500 mg / m ² Gallic acid propyl ester 300 mg / m ² Styrene-maleic acid copolymer 100 mg / m ² Alkali-treated gelatin (isoelectric point 4.9) 1.0 g / m ² Formalin 10 mg / m ² Polyacrylamide 500 mg / m ² After adjusting the pH to 5.4 with citric acid, it was applied.

Next, on the support opposite to the emulsion layer, an antistatic layer and a backing layer were provided in exactly the same manner as in Example 2. However, formalin was used as a hardening agent for the backing layer at this time.

 Processing and evaluation were performed in the same manner as in Example 2.

However, the following developer was used. Table 3 shows the obtained results.

(Composition A) Pure water (ion-exchanged water) 150 ml Disodium ethylenediaminetetraacetate 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 1-phenyl-3-pyrazolidone 0.5 g 1-phenyl- 5-mercaptotetrazole 30mg Potassium hydroxide Amount to adjust the pH of the working solution to 10.4 Potassium bromide 4.5g (Composition B) Pure water (ion exchange water) 3mg Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3 The above composition A and composition B were dissolved in 500 ml of water in the order of use when using a ml developer, and finished to 1 before use.

From the results shown in Table 3, as in the case of the hydrazine compound of Example 2, the sample of the present invention shows little decrease in sensitivity due to storage over time and little deterioration in antistatic ability after treatment.

〔The invention's effect〕

The present invention has an antistatic layer having excellent transparency without haze, and the surface resistivity is less deteriorated with time even with the use of a super-high contrast agent such as a tetrazolium compound or a hydrazine compound, and is not desensitized. Thus, a silver halide photographic light-sensitive material having high stability could be provided.

Continuation of the front page (56) References JP-A-61-174542 (JP, A) JP-A-60-185947 (JP, A) JP-A-61-249047 (JP, A) JP-A-63-314541 (JP) , A) JP-A-58-63933 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/85 G03C 1/06

Claims (1)

(57) [Claims] 1. A silver halide photographic photosensitive material having a photosensitive emulsion layer on a plastic film support having an antistatic layer comprising a reaction product of a water-soluble conductive polymer, hydrophobic polymer particles and a curing agent. In the material, the hydrophobic polymer particles are composed of styrene and an alkyl acrylate and / or alkyl methacrylate having 1 to 12 carbon atoms, are dispersed and stabilized by a nonionic surfactant having 3 or more alkylene oxide chains, and A silver halide photographic light-sensitive material characterized in that the emulsion layer contains a tetrazolium compound or a hydrazine compound.