JPH0359645A - Silver halide photographic sensitive material subjected to antistatic treatment - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material which has a hazeless antistatic layer having excellent transparency by dispersing and stabilizing hydrophobic polymer particles as a cyano group-contg. latex into the antistatic layer. CONSTITUTION:The hydrophobic polymer particles are dispersed and stabilized as the cyano group-contg. latex in the antictatic layer of a plastic film supporting body formed by having the antistatic layer consisting of the reaction product of a water soluble conductive polymer, the hydrophobic polymer particles and a hardener. Thus, the silver halide photographic sensitive material which has the hazeless antistatic layer having the excellent transparency, is less deteriorated in surface specific resistance and is not desensitized with the lapse of time in spite of using a super high-contrast agent, such as tetrazolium comped. or hydrazine compd., and has high stability is obtd..

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an antistatic layer for a plastic film support, and more particularly to a silver halide photographic material with excellent antistatic ability.

[Background of the invention]

Generally, plastic film supports have strong electrostatic properties, and this often imposes many restrictions on their use. For example, supports such as polyethylene terephthalate are generally used in silver halide photographic materials;
It is easy to be charged especially in low humidity such as winter. Antistatic measures are especially important when high-speed photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed to light using automatic printers, as has been the case recently.

When a photosensitive material is charged, static marks appear due to the discharge, or foreign matter such as dust adheres to it, which causes pinholes and significantly degrades the quality, making it extremely difficult to repair. I'll put it down. For this reason, antistatic agents are generally used in photosensitive materials, and recently, fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, and sulfonic acid Alternatively, a polymer having a phosphoric acid group in the molecule is used.

In particular, adjusting the charge series using fluorine-based surfactants or improving conductivity using conductive polymers has been widely used, for example, in JP-A-49-91165 and JP-A-49-1.
No. 21523 discloses an example in which an ionic polymer having a dissociative group in the polymer main chain is applied.

However, in these conventional techniques, the antistatic ability is significantly deteriorated by the development process.

This is thought to be because the antistatic ability is lost through processes such as a developing process using an alkali, an acidic fixing process, and washing with water. Therefore, when a processed film is further used for printing, such as with printing photosensitive materials, problems such as pinholes occur due to adhesion of dust.

For this reason, for example, JP-A Nos. 55-84658 and 61-1
No. 74542 proposes an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine. Although this method allows antistatic properties to remain after treatment, it is still insufficient in terms of transparency.

Furthermore, when an ultra-high contrast emulsion using a tetrazolium compound or a hydrazine compound is applied to a plastic film support having an antistatic layer, it has been found that the emulsion becomes desensitized during storage over time.

[Purpose of the invention]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic material having an antistatic layer with excellent transparency and no haze.A further object of the present invention is to provide a silver halide photographic material having an antistatic layer with excellent transparency and no haze. It is an object of the present invention to provide a silver halide photographic light-sensitive material which has excellent antistatic ability even when used and is highly stable without desensitization over time.

[Structure of the invention]

The above object of the present invention is to provide a plastic film support having an antistatic layer consisting of a reaction product of (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (2) a curing agent.
This is achieved by a silver halide photographic material having an antistatic layer characterized in that the hydrophobic polymer particles are dispersed and stabilized in the antistatic layer as a cyano group-containing latex.

Incidentally, it is desirable that the photosensitive emulsion layer of the present invention contains a tetrazolium compound or a hydrazine compound.

The details of the present invention will be explained below.

Although the water-soluble conductive polymer of the present invention can form a transparent layer when used alone, a slight fluctuation in drying conditions may cause cracks in the layer. The structure of the present invention contains hydrophobic polymer particles to prevent cracking, and the effect is significant.

The water-soluble conductive polymer according to claim 1 of the present invention has at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, and a polyethylene oxide group. Examples include polymers with Among these groups, sulfonic acid groups, sulfuric acid ester groups, and quaternary ammonium bases are preferred.

The amount of conductive groups required is 5% by weight or more per polymer molecule. Carboxy groups, hydroxy groups, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups contained in water-soluble conductive polymers,
Among vinyl sulfone groups, carboxy groups, hydroxy groups, amino groups, epoxy groups, aziridine groups, and aldehyde groups are preferred.

These groups are required in an amount of 5% by weight or more per polymer molecule. The molecular weight of the polymer is 3,000 to 100,000, preferably 3,500 to 50,000.

Examples of water-soluble conductive polymer compounds used in the present invention are listed below, but the present invention is not limited thereto.

A-1 homopolymer -2 homopolymer KoLJ, Na 3 -5 03Na -6 SO, Na -7 SO, Na -8 -9 -10 CH.

1 a 03Na 2 3 CH3 -14 C1120SO3Na -15 -17 19 0 -21 -22 Na10,000 M'+15,0003 Dextran sal 7-eight substitution degree 2.0 M -100,000-24 -25 6 SO, Na 7 - OINa 9 0 -31 2 -33 -34 SO. Na 35 -36 8-37 8 -39 -40 -41 2 I3 M#10,000-43 4 5 x:y:z:w-40:30:20:10-47 8 -49 -50 M#50,000 In addition, in the above (1) to (50), x, y, and z each represent the mol% of the monomer component, and M represents the average molecular weight (in this specification, the average molecular weight refers to the number average molecular weight). represents.

These polymers can be synthesized by polymerizing heptamers that are commercially available or obtained by conventional methods. The amount of these compounds added is preferably 0.01 g"log/-, particularly preferably 0.1 g/m to 5 g/m".

Next, the hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are contained in a so-called latex form that is substantially insoluble in water. These hydrophobic polymers include cyano group-containing styrene, styrene derivatives, alkyl acrylates, and alkyl methacrylates. In particular, it is preferable that at least 30 mol% of a cyano group-containing styrene derivative, alkyl acrylate, or alkyl methacrylate is contained. Particularly preferred is 50 mol% or more.

There are two methods to make a latex from a hydrophobic polymer: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent and finely dispersing it, followed by distilling off the solvent. t: Emulsion polymerization is preferred in terms of the ability to produce products.

As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant.
It is preferably 0% by weight or less. A large amount of surfactant causes clouding of the conductive columnar layer.

If the molecular weight of the hydrophobic polymer is 3000 or more, specific examples of the hydrophobic polymer of Yoshiki's invention will be given.

-6 B-11 In the present invention, a conductive layer is coated on a transparent support. Although any photographic transparent support can be used, polyethylene terephthalate or cellulose triacetate, which is made to transmit 90% or more of visible light, is preferable.

These transparent supports are prepared by methods well known to those skilled in the art, but in some cases, a slight amount of dye may be added to give them a blue tint so as not to substantially inhibit light transmission. good.

The support of the present invention may be coated with a subbing layer containing a latex polymer after being subjected to a corona discharge treatment. In the corona discharge treatment, In+W~l k
W/mzmrn is particularly preferably applied.

Particularly preferably, corona discharge treatment is performed again after coating the latex undercoat layer and before coating the conductive column layer.

As the compound for curing the conductive layer of the present invention, polyfunctional aziridine is preferred. Particularly preferred are those having bifunctional or trifunctional properties and a molecular weight of 600 or less.

The conductive layer of the present invention may be located on the side of the support from the photosensitive layer, or on the opposite side of the support with respect to the photosensitive layer.The hydrazine compound used in the present invention is preferably represented by the following general formula [H]. It is a compound that is

General 2 (H) QI Q! Xl I R, -N -N -C-R2 In the formula, R1 represents a monovalent organic residue, R2 represents a hydrogen atom or a monovalent organic residue, Q and Q2 are a hydrogen atom,
Alkylsulfonyl group (including those with substituents),
It represents an arylsulfonyl group (including one having a substituent), and Xl represents an oxygen atom or a sulfur atom. Among the compounds represented by the general formula (H), compounds in which X is an oxygen atom and R2 is a hydrogen atom are more preferred.

The monovalent organic residues for R8 and R3 include aromatic residues, heterocyclic residues, and aliphatic residues.

Aromatic residues include phenyl groups, naphthyl groups, and substituents thereof (for example, alkyl groups, alkoxy groups, acylhydrazino groups, dialkylamino groups, alkoxycarbonyl groups, cyan groups, carboxy groups, nitro groups, alkylthio groups, and hydroxy groups). , sulfonyl group, carbamoyl group, halogen atom, acylamino group, sulfonamide group,
urea group, thiourea group, etc.). Specific examples of those with substituents include 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-tert-butylphenoxy)butyramide 1
Examples include phenyl group, 4-[2-(2,4-di-tert-butylphenoxy)butyramide 1 phenyl group, and the like.

The heterocyclic residue is a membered or six-membered monocyclic or condensed ring having at least one of oxygen, nitrogen, sulfur, or selenium atoms, and a substituent may be attached thereto.

Specifically, for example, biroline ring, pyridine ring, gynoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring,
Examples include residues such as a benzoselenazole ring and a naphthoselenazole ring.

These heterocycles have 1 to 4 carbon atoms, such as a methyl group or an ethyl group.
Alkyl group, methoxy group, ethoxy group, etc. having 1 to 4 carbon atoms
may be substituted with an alkoxy group of phenyl Me, an aryl group having 6 to 18 carbon atoms, a halogen atom such as chloro or bromine, an alkoxycarbonyl group, a cyano group, an amino group, or the like.

Aliphatic residues include linear and branched alkyl groups, cycloalkyl groups, and those with substituents, as well as alkenyl groups and alkynyl groups.

Straight-chain and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
18, preferably an alkyl group of 1 to 8, and specific examples include a methyl group, ethyl group, isobutyl group, l-octyl group, and the like.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as cyclopropyl, cyclohexyl, adamantyl, and the like. Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkylthio groups, amide groups, acyloxy groups,
Cyano group, sulfonyl group, halogen atom (e.g. chlorine,
bromine, fluorine, iodine, etc.), aryl groups (e.g., phenyl group, halogen-substituted phenyl group, alkyl-substituted phenyl group), etc. Specific examples of substituted groups include 3
-methoxypropyl group, etquin carbonylmethyl group,
Examples include 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, and p-chlorobenzyl group. In addition, examples of alkenyl groups include allyl (a
Examples of the alkynyl group and the alkynyl group include a propargyl group.

The present invention Preferred specific examples of dorazine compounds As shown below, The invention is in no way limited thereby. It's not something you can do.

− -3 − 6 1 -10 -13 4 6- 8 −19 0 1 −22 3 4 -25 Cl(.

H3 H-26 H-30 -31 -34 -35 -38 -39 0 -41 -42 -43 H-44 H-45 -46 The addition position of the hydrazine compound represented by general formula ()f) is silver halide The emulsion layer and/or the non-photosensitive layer on the side of the silver halide emulsion layer on the support, preferably,
The silver halide emulsion layer and/or its lower layer. The amount added is preferably 10-' to 10-' mol/silver 1 mol,
More preferably, it is 10-4 to 1°-2 mole/I mole of silver.

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

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

General formula (T) In the present invention, substituent R1 of the phenyl group of the triphenyltetrazolium compound represented by the above general formula (T),
R2 and R3 are preferably hydrogen atoms or those having a negative or positive Hammett's sigma value (σP) indicating the ability to attract electrons.

In particular, negative ones are preferred.

Hammett's sigma values for phenyl substitution have been reported in many publications, such as the Journal of Medical Chemistry.
Medical Chemistry) No. 20
Vol. 304, 1977, as described by C. Hanks (C.

Particularly preferred groups having negative sigma values include, for example, the methyl group (σP--0.17 or less, all aP values), the ethyl group (
-0,15), cyclopropyl group (-0,21), n-
Glopyl group (-0,13), isopropyl group (-0,
15), cyclobutyl group (-0,15), n-butyl group (-0,16), 1sO-butyl group (-0,20), n
-pentyl group (-0,15), cyclohexyl group (-0
, 22), amino group (-0,66), acetylamino group (-0,15), hydroxyl group (-0,37), methoxy group (-0,27), ethoxy group (-0,24), Propoxy group (-0,25), butoxy group (-0,32)
, pentoxy group (-0,34), etc., and these are all useful as It substituents in the compound of general formula (T) of the present invention.

Specific examples of the compound of general formula (T) used in the present invention are listed below, but the compound of the present invention is not limited thereto.

The tetrazolium compound used in the present invention is described in, for example, Chemical Review (Chemical Review).
s) It can be easily made into synthetic leather according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound of the present invention is a halogen compound of the present invention.
It is preferably used in an amount of about 1 mg or more, preferably about 1 mg or more, up to about 2 g per mole of silver halide contained in the silver photographic material.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any commonly used silver halide grains can be used, and the silver halide grains may be those obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is formed inside the particle.

The silver halide emulsion used in the present invention is, for example, US Pat. No. 2,444.607, US Pat. No. 2,716.062, US Pat.
No. 89,380, No. 2,058,626, No. 2,
118.411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342,596, Japanese Patent Publication No. 4417-1987, West German Application Publication No. 2,149,789, Japanese Patent Publication No. 39-2
Compounds described in specifications or publications such as No. 825 and Japanese Patent Publication No. 49-13566, preferably, for example, 5°6-drimethylene-7-hydroxyne-S-triazolo (1,5-a)pyrimidine, 5. 6-tetramethylene 7-hydroxy-s-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-5-1lyazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-5- Triazolo (1,5-a)pyrimidine, 7-
Hydroxine-3-) Riazolone (1,5-a) Pyrimidine, 5-methyl-6-bromo-hydroxy-s-
Triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (l-phenyl-5-mercaptotetrazole, 2-
It can be stabilized using mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-nidropenzimidazole), and the like.

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

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

A hydrophilic colloid used with particular advantage in the present invention is gelatin.

The gelatin used in the present invention can be treated with either alkali treatment or acid treatment, but when using ossein gelatin, it is preferable to remove calcium or iron. The preferred calcium content is 1-99
The iron content is preferably 9 ppm, more preferably 11-500 ppm, and the iron content is preferably 0.001-50 ppm, still more preferably 00-1-1 Opp. The method of adjusting the amounts of calcium and iron in this way can be distantly related by passing an aqueous gelatin solution through an ion exchange device.

Developing agents used in developing the silver halide photographic material according to the present invention include catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2
, 3-dibromohydroquinone, 2.5-diethylhydroquinone, catechol, 4-riO-locatechol, 4-
Phenyl-catechol, 3-methoxy-catechol, 4
-Acetyl-pyrogallol, sodium ascorbic acid, etc.

In addition, as HO-(CH-CH), -NH, type developers, ortho and rose aminophenols are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-amino- Examples include 4-chloro-6-phenylphenol and N-methyl-p-aminophenyl.

Furthermore, examples of 82N-(CH-CH), -NH, type developers include 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N-( Examples include 4-amino-3-methylphenyl)-morpholine and p-phenylenediamine.

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 include l-phenyl-4-amino-5-pyrazolone and 5-aminoraunol.

The Theory of the Photographic Process, 4th Edition, by T. H. James.
ic Process Fourth Edition)
pp. 291-334 and Journal of the American Chemical Society.
he American Chemical
Ety) Vol. 73, p. 3.100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material according to the invention, the effects of the invention will not be impaired. In addition, hydroxylamine and hydrazide compounds can be used as preservatives, and in this case, the amount used is preferably 5 to 500 g per 1Q of developer.
More preferably, it is 20 to 200 g.

Further, the developer may contain glycols as an organic solvent, and such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-bentanediol, etc. However, diethylene glycol is preferably used. The preferred amount of these glycols used is 5 to 500 per developer 11+.
g, more preferably 20 to 200 g. These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material according to the present invention can be developed with a developer containing the above-mentioned development inhibitor to obtain a light-sensitive material with extremely excellent storage stability.

The pH value of the developer having the above composition is preferably 9 to 13.
However, from the viewpoint of storage stability and photographic properties, the pH value is 1O~1
A range of 2 is more preferred. Regarding cations in the developer, it is preferable that the ratio of potassium ions is higher than that of sodium 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 less, particularly preferably around 25°C to 40°C, and the developing time is generally completed within 2 minutes, particularly preferably 10 seconds to 40°C. 50 seconds often produces good results. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these processes can be carried out using so-called manual development processes such as plate development and frame development, roller development,
Mechanical development such as hanger development may be used.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples.

It should be noted that, as a matter of course, the present invention is not limited to the embodiments described below.

Example! 8 w/ to subbed polyethylene terephthalate
After corona discharge with energy of m”min, apply antistatic liquid with the following composition at 30m/n+in in the amount shown below.
The coating was applied using a roll-fit coating pan and an air knife at a speed of .

Water-soluble conductive polymer (A) 0.6g/
m” Hydrophobic polymer particles of the present invention (B) 0.4
g/m2 Hardener (H) Dry at 90°C for 12 minutes and heat treated at 140°C for 190 seconds.

Gelatin was coated on this antistatic layer at a concentration of 2°Og/+n" and a haze test was conducted. As a hardening agent for gelatin, formalin, 2,4-dichloro-6-bitroxy-S-triazine, Sodium was used. The results are shown in Table 1.

(Haze test) Turbidity meter Model T-260OD manufactured by Tokyo Denshoku Co., Ltd.
From the results in the table described in JP-A No. 55-84658, it can be seen that the samples of the present invention are excellent in haze.

Example 2 (Preparation of an emulsion) A rhodium salt containing 10-' mol per mol of silver and having an average grain size of 0.05 mm was prepared by the Chondrold double-jet method in an acidic atmosphere at pH 3.0. llpm, /' Silver chlorobromide grains having a silver halide set composition dispersity of 15 and containing 5 mol % of silver bromide were prepared. The growth of particles was carried out in a system containing 30 mg of benzyladenine per 1 Q of a 1% aqueous gelatin solution. After mixing silver and halide, 6-methyl-4-hydroxy-1,3,3a,7tetrazaindene was added to silver halide 1
600 mg per mole was added, and then washed with water and desalted.

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

Additives were added to the obtained emulsion in the amounts shown below, and the mixture was coated on a polyethylene terephthalate support having a thickness of 1100 p that had been subjected to latex subbing treatment according to Example 1 of JP-A-59-19941.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer 1.0 g/m"Tetraphenylphosphonium chloride 30 mg/11"Saponin 200 mg/m"
Polyethylene glycol 100 mg/m”
Hydroquinone 200 mg/+
"Styrene-maleic acid copolymer 20 mg/m"
Hydrazine compound (shown in Table 2) 50 mg/m
25-methylbenzotriazole 30 mg/m
2 Desensitizing dye (M) 20 mg
/m2 Alkali-treated gelatin (isoelectric point 4.9) 1.5
g/m' bis(vinylsulfonylmethyl)ether 15 mg
/m'' Silver amount: 2.8 g/m'' (emulsion layer protective film) An emulsion layer protective film was prepared in the amount shown below and coated simultaneously with the emulsion in a multilayer manner.

Fluorinated dioctyl sulfosuccinate ester 200mg/
m' Sodium dodecylbenzenesulfonate 100B/m' Matting agent: Polymethyl methacrylate (average particle size 3° 5μ
m) 100 B/a" lithium nitrate salt 30 □/- gallic acid-propyl ester 300 mg/m2-mercagutobenzimidazole-5-sodium sulfonate 30 mg/m" alkali-treated gelatin (isoelectric point 4.9 ) 1.3 g/m" Colloidal Silica 30 n+g/m" Suguruen-Malein H both I! Combined 100 n+g/m
”Bis(vinylsulfonylmethyl)ether 15 m
g/m” Next, on the support opposite to the emulsion layer, 30 g/m”
After corona discharge with a power of W/s”min, poly(styrene-butyl acrylate-glycidyl methacrylate) latex polymer was applied in the presence of hexamethylene aziridine hardener and an antistatic layer was applied as in Example 1. Then, a backing layer having the following composition was prepared and applied so that the amount of additives was as shown below.

(Backing layer) Latex polymer: Butyl acrylate-styrene copolymer 0.5 g/m" Styrene-maleic acid copolymer 100 mg/m" Citric acid (adjusted to pH 5.4 after coating) 40 mg 7m2 Saponin
200 mg/m" King dye (a) (b) (c) Alkali-treated gelatin 2.0 g/m" Bis(vinylsulfonylmethyl) ether t5 mg/+" (Backing layer protective film) Add the following amounts of additives: It was prepared in the same manner and applied in a multilayer manner on top of the green layer.

Dioctylsulfosuccinate ester packaging 200 mg/m” Matting agent: Polymethyl methacrylate (average particle size 4.0 μff1) 50
mg/m'alkali-treated gelatin (isoelectric point 4.9) 1
．． 0g/m' Sodium fluorinated dodecylbenzenesulfonate 50 mg/m'
Bis(vinylsulfonylmethyl) ether 20 mg/m”
Note that the pH of the coating solution was adjusted to 5.4 in advance before coating.

Divide each sample obtained as above into two,
One was stored for 3 days at 23°C and 55% relative humidity. The remaining one was conditioned for 3 hours at 23° C. with relative humidity of 55%, sealed in a moisture-proof bag in a stacked state, and stored at 55° C. for 3 days to undergo forced deterioration to create an aging sample.

After both samples were exposed through a step wedge and developed using the developer and fixer shown below, sensitivity and surface resistivity were determined. The sensitivity is 1.0 in terms of optical density.
The exposure amount is expressed as relative sensitivity. The results are shown in Table 2.

Development processing conditions Process Temperature Time Development 34°O 15 seconds fixation 32°0 10 seconds water washing Room temperature 10 seconds Developer formulation Hydroquinone 25 gl-7
enyl 4.4 dimethyl-3 pyrazolidone 0.4 g sodium bromide 3 g 5-methylbenzotriazole 0.3 g 5-nitroindazole
0.05g diethylaminopropane-1,2-
Diol 0 g Potassium sulfite 0 Sodium 5-sulfosalicylate 5 Sodium ethylenediaminetetraacetate Finished to 112 with water.

The pH is 11.5 with caustic soda. Fixer formulation (Group fRA) Ammonium thiosulfate (72.5w% Shi　Iko　.

aqueous solution) 240 mo 7 g 6.5 g g g 13 , 6 m (2 Sodium sulfite sodium acetate, trihydrate boric acid, sodium citrate, dihydrate acetic acid (90w% aqueous solution) 11) Pure water (ion exchange water) Sulfuric acid ( 50W% aqueous solution) Aluminum sulfate (Aff, O, converted content is 8.1w%)
Aqueous solution of 17fflI2 4.7g 26.5g When using a fixer, the above composition A1 was dissolved in 500ml of water (2) in the order of composition A1 and finished as Q.

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

Example 3 In the same manner as in Example 2, rhodium salt was added in l/mol of silver.
Silver chlorobromide particles containing 2 mol % of silver bromide with an average particle diameter of 0.20 μm and a monodispersity of 20 were prepared.

This was desalted and sulfur sensitized in the same manner as in Example 2.

Additives were added to the obtained emulsion in the amounts shown below, and the mixture was coated on the undercoated polyethylene terephthalate support used in Example 1.

Latex polymer: Styrene-butyl acrylate acrylic acid ternary copolymer polymer 1.0g/m”phenol
l mg/m”saponin
200mg/m" Sodium dodecylbenzenesulfonate 50mg/m" Tetrazolium compound (shown in Table 3) 50mg/m'
Compound (N) Compound (0) Styrene-maleic acid copolymer alkali-treated gelatin (isoelectric point 4.9) Silver amount Formalin 40 mg/m" 50 mg/□2 20 mg/m2 2.0 g/m" 3.5 g/ m2 10 mg/m' Compound (O) The coating solution was coated after adjusting the pH to 6.5 with sodium hydroxide in advance. As an emulsion protective film, additives were prepared in the amounts shown below and were coated simultaneously with the emulsion coating solution.

Fluorinated dioctyl sulfosuccinate 100mg/m"Dioctyl sulfosuccinate 100mg/m"Matting agent: Amorphous silica 50mg/m"Compound (0) 30mg/m"
5-methylbenzotriazole 20mg/m
'Compound (P) 500mg/m'' Gallic acid propyl ester 30On+g/m
"Styrene-maleic acid copolymer 100mg/
m” alkali-treated gelatin (isoelectric point 4.9) 1.
Og/m” formalin lo
mg/m2 polyacrylamide 500
The pH was adjusted to 5.4 with citric acid before coating.

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

It was treated and evaluated in the same manner as in Example 2.

However, the following developer was used. The results obtained are shown in Table 3.

(Composition A) Pure water (ion exchange water) l 50mf
f Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (55% w/v aqueous solution) 100ml 12 Potassium carbonate 50g hydroquinone 15g 1-phenyl-3
-Pyrazolidone 0.5g1-phenyl-
5-Mercaptotetrazole 30mg Potassium hydroxide Amount to bring the pH of the working solution to 10.4 Potassium bromide
4.5 g (Composition B) Pure water (ion-exchanged water) 3 mg Diethylene glycol 50 g Ethylenediaminetetraacetic acid dinatrilam salt 5 mg Acetic acid (90% aqueous solution) 0.3 m2 When using a developer, add the above group J*A in 500 mI2 of water.

The results in Table 3 also show that, as in the case of the hydrazine compound of Example 2, the samples of the present invention show little decrease in sensitivity due to storage over time, and little deterioration in antistatic ability after treatment.

〔Effect of the invention〕

The present invention has an antistatic layer with excellent transparency without haze, and even when ultrahigh contrast agents such as tetrazolium compounds or hydrazine compounds are used, there is little deterioration in surface resistivity over time and there is no desensitization. , it was possible to provide a highly stable silver halide photographic material.

Claims (2)

[Claims] (1) A plastic film support comprising an antistatic layer comprising a reaction product of [1] a water-soluble conductive polymer, [2] hydrophobic polymer particles, and [3] a curing agent,
1. A silver halide photographic material having an antistatic layer, wherein the hydrophobic polymer particles are stabilized as a cyano group-containing latex dispersed in the antistatic layer. (2) A silver halide photographic light-sensitive material, characterized in that the light-sensitive emulsion layer according to claim 1 contains a tetrazolium compound or a hydrazine compound.