JPH0359640A - 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 substd. azirdine group-contg. latex into the antistatic layer. CONSTITUTION:The hydrophobic polymer particles are dispersed and stabilized as the substd. aziridine group-contg. latex in the antistatic layer of a plastic film base 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 compd. or hydrazine compd., and has high stability is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antistatic layer for a plastic film support, and more particularly to a silver 10 degenide photographic light-sensitive material having 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, adjustment of the charge series using a heptadium-based surfactant or improvement of conductivity using a conductive polymer has been widely used, for example, in JP-A-49-91165 and JP-A-49-91165.
No. 121523 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, it has been found that when an ultra-high contrast emulsion using a tetrazolium compound or a hydrazine compound is applied to a plastic film support having this antistatic layer, it has the disadvantage of desensitization 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 latex containing a substituted aziridine group.

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 3 -5 SO, Na 5O8Na -7 -9 -10 1 ff 2 A-13 CH.

So, K 4 CHzO503Na -15 CH.

−17 A-19 A-20 -21 2 M#10,000 M humiliation 15,000 3 Dextranthal 7ei to Degree of substitution 2.0 M - 100,000 4 5 -26 So3Na -27 8 o3Na 9 -30 -31 2 -33 03Na −34 So, Na A-35 A-36 -37 8 9 -40 -41 -42 SO, Na M″410,000 M#30,000 3 -44 -45 6 CH.

x:y:z:w-40:30:20:10M″q50,000-47-48-49-50 M#50,000In addition, in (1) to (50) above, x, y, and z are each a single unit. M represents the mol% of the mer components, and M represents the average molecular weight (in this specification, the average molecular weight refers to the number average molecular weight).

These polymers can be prepared by polymerizing heptamers which are commercially available or obtained by conventional methods. The amount of these compounds added is preferably O, O1g=1Qg/m2, particularly preferably 0.1g to 5g/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. This hydrophobic polymer is made of seven polymers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, hinyl ester derivatives, acrylonitrile, etc. in any combination. Obtained by polymerizing. In particular, it is preferable that at least 0.1 mol % of a heptamine having a substituted aziridine group is contained. Particularly preferred is 0.5 mol% or more.

There are two methods to make a hydrophobic polymer into a latex form: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent, finely dispersing it, and then distilling off the solvent. Emulsion polymerization is preferable because it can produce a product.

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 layer.

The molecular weight of the hydrophobic polymer may be 3000 or more,
There is almost no difference in transparency depending on molecular weight.

Specific examples of the hydrophobic polymer of the present invention will be given below.

-5 -6 -8 -9 H 2 -13 CH.

4 CH.

5 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. Corona discharge treatment has an energy value of 1 mW −1k
W/m2m1n is particularly preferably applied.

Particularly preferably, corona discharge treatment is performed again after applying the latex undercoat layer and before applying the conductive 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 closer to the support than the photosensitive layer, or the hydrazine compound used in the present invention may be located on the opposite side of the support from the photosensitive layer. It is a compound that is

General formula (H) QI Ql Xl 1 R, -N -N -C-R2 In the formula, R1 represents a monovalent organic residue, R2 represents a hydrogen atom or a monovalent organic residue, and Ql and Q2 is 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 [I], compounds in which Xl is an oxygen atom and R2 is a hydrogen atom are more preferred.

The monovalent organic residues for R1 and R2 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, cyano 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 M, 4-oxyethylphenyl group, 4-)'decylphenyl group, 4-carboxyphenyl group, 4-diethylaminophenyl! , 4-octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2-methylphenyl group, 4-(
3-ethylthioureido) phenyl group, 4-[2-(2
, 4-di-tert-butylphenoxy)butyramide] phenyl group, and 4-[2-(2,4-di-tert-butylphenoxy)butyramide] phenyl group.

The heterocyclic residue is a five- or six-membered monocyclic ring or fused 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, quinoline 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.jl[l[1
-4 alkoxy groups, aryl groups having 6 to 18 carbon atoms such as phenyl groups, halogen atoms such as chloro and bromine, alkoxycarbonyl groups, cyano groups, amino groups, etc. may be substituted.

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, carbon atoms with 1-
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 a cyclopropyl group, a nclohexyl group, and an adamantyl group. 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
-methoxyglobil group, ethoxycarbonylmethyl 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.

− -2 − -4 − 6 − -10 -13 -14 H-16 -18 -19 1■ 20 -21 -22 -23 -24 -25 CH.

H3 I] 26 0 1 4 I'I3 5 7 +(-38 -39 Csl(++(L) -40 -41 -42 -43 n3 44 I] 5 -46 Hydrazine represented by general formula (H) The compound is added to the silver halide emulsion layer and/or the non-photosensitive layer on the side of the silver halide emulsion layer on the support, but preferably,
The silver halide emulsion layer and/or its lower layer. The amount added is preferably 10-'-10-' mole/1 mole of silver,
More preferably, it is io-' to 102 moles/1 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),
R3 and R1 are preferably hydrogen atoms or those having a negative or positive Hammett's sigma value (yP) 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
Volume, 304 pages, 1977, C.
.

Particularly preferable groups having negative sigma values include, for example, methyl groups (σP--0.17 or less, all σP values), ethyl groups (
-0,15), cyclopropyl group (-0,21), n-
Propyl 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), ami7 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), and the like, all of which are useful as substituents for the compound of general formula (T) of the present invention.

Specific examples of the compound of the general formula [T] used in the present invention are listed below, but the compounds of the present invention are not limited thereto.

(Exemplary Compounds) The tetrazolium compounds used in the present invention are described, for example, in Chemical Raviaw.
s) It can be easily synthesized according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound of the present invention is preferably used in an amount of about 1 mg to about 10 g, preferably about 1 mg to about 2 g, per mole of la 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 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 mainly inside the particle.

The silver halide emulsion used in the present invention can be used, for example, in U.S. Pat. No. 2,444,607, U.S. Pat.
No. 189.380, 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. 47-4417,
West German Application Publication No. 2,149.789, Special Publication No. 1973-
Compounds described in specifications or publications such as No. 2825 and Japanese Patent Publication No. 49-13566, preferably, e.g.
゜6-drimethylene-7-hydroxyne-s-triazolo (1,5-a) pyrimidine, 5,6-titramethylene-7-hydroxy-s-triazolo (1,5-a)
Pyrimidine, 5-methyl-7-hydroxy-5-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxyS-triazolo(1,5-a)pyrimidine, 7
-Hydroxyne-5-triacylon(1,5-a)pyrimidine, 5-methyl-6-promorph-hydroxy-S
- triazolo(1,5-a)pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodecyl gallate,
propyl gallate, sodium gallate), mercaptans (l-phenyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-nidrobenzimitazole), etc. can be stabilized.

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 nohydroquinone, or an inhibitor such as benzotriazole can 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
9ppm, more preferably 500ppm, and iron content is preferably 0.001-50ppm, more preferably 0.1-1Oppm.The method for adjusting the amount of calcium and iron in this way is as follows: This can be achieved 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-dibromo/hydroquinone, 2,5-diethylhydroquinone, catechol, 4-chlorocatechol, 4
-phenyl-catechol, 3-methoxy-catechol,
Examples include 4-acetyl-pyrogallol and sodium ascorbic acid.

Further, as the HO-(CH-CI), -NHz type developer, ortho and rose aminophenols are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4 -chloro-6-phenylphenol, N-methyl-p-aminophenyl, and the like.

Furthermore, examples of H,N-(CH-CH), -NH2 type developers include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N- Examples include (4-amino-3-methylphenyl)-7-ruforine and p-7z nylene diamine.

Examples of heterocyclic developers include -pyrazolidones,
Examples include l-7enyl-4-amino-5-pyrazolone and 5-aminolaucil.

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 5oci
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. Further, hydroxylamine or a hydrazide compound can be used as a preservative, and in this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g, per developer Iff.

Further, the developer may contain glycols as an organic solvent, and examples of such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol,
Although examples include 1,5-bentanediol, diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 20 to 200 g per 1Q of developer solution. 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'O or lower, particularly preferably around 25°C to 40°C, and the development time is generally completed within 2 minutes, particularly preferably 10 seconds. ~50 seconds often produces good results. In addition, processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening,
It is optional to employ steps such as neutralization, and these can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔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 1 Subbing treated polyethylene terephthalate at 8 v/
After corona discharge with energy of m'・min, apply antistatic liquid of the following composition at 30 m/min to the following amount.
It was applied using a roll-fit coating hand 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/m'' Hardener (H) It was dried at 90'C for 2 minutes and heat treated at 140°C for 190 seconds.

Gelatin was coated on this antistatic layer at a concentration of 2.0 g/m'' and a haze test was conducted.As a hardening agent for gelatin, formalin, 2,4-dichloro-6-hydroxy/
-3-) using lyazine 1 helium; Table 1 shows the results.
Shown below.

(Haze test) Turbidity meter Model T-2600D 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 emulsion) A rhodium salt was prepared by a controlled double jet method in an acidic atmosphere at pH 3.0, containing 104 mol of rhodium salt per mol of silver, an average grain size of 0.1177 m, and a silver halide composition monodispersity of 15. , silver chlorobromide grains containing 5 mol % of silver bromide were prepared. Particle growth was carried out in a system containing 30 mg of benzyladenine per 1% aqueous gelatin solution IQ. After mixing silver and halide, 6=methyl-4-hydroxy-1
, 3,3a, 7-tetrazaindene was added in an amount of 600 mg per mole of silver halide, followed by washing with water and desalting.

Then, 60 mg of 6=methyl-4-hydroxy-1,3,3a,7-tetrazaindene per mole of silver halide was added, followed by 15 mg of sodium thiosulfate per mole of silver halide, and the mixture was heated at 600C. Sulfur sensitized. 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 resulting emulsion in the amounts shown below, and the mixture was coated on a 100 μm thick polyethylene terephthalate support that had been subjected to latex subbing treatment according to Example 1 of JP-A-59-19941.

Latex polymer: styrene-butyl acrylate
Acrylic acid tertiary copolymer polymer l・Og/m" Tetraphenylphosphonium chloride 30 mg/m2 Saponin 200 mg/m" Polyethylene glycol 100 mg/m"
Hydroquinone 200 mg/m”
Styrene-maleic acid copolymer 20 mg/m" Hydrazine compound (shown in Table 2) 50 mg/m2
5-methylbenzotriazole 30 mg/m”
Desensitizing dye (M) 20 mg/
m” 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 3.5/J m) 100
mg/m” lithium nitrate salt 30
mg/m” gallic acid globyl ester 300
mg/m” Sodium 2-mercaptobenzimidazole-5-sulfonate 30 mg
/m” Alkali-treated gelatin (isoelectric point 4.9) 1.3
g/m2 colloidal silica 30
mg/m” styrene-maleic acid co-T11 combination 100
mg/m" bis(vinylsulfonylmethyl)ether 15 mg/m2 Next, 30 mg/m" bis(vinylsulfonylmethyl)ether
After corona discharge with a power of W/m”min, coating was carried out in the presence of poly(styrene-butyl acrylate-glycidyl methacrylate tyrene aziridine hardener) and an antistatic layer was coated as in Example 1, followed by the following coating. A backing layer having the 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/m2 Styrene-maleic acid copolymer 100 mg/m2 Citric acid (adjusted to pH 5.4 after coating) 40 mg/m2 Saponin
200 mg/m2 Lithium nitrate 30 mg/m2 Backing dye (a) (b) (c) Alkali-treated gelatin 2.0 g/m" Bis(vinylsulfonylmethyl) ether 15n+g/m" (backing layer protective film) Additives were prepared in the amounts shown below and were simultaneously coated on top of the glue layer.

Dioctylsulfosuccinate ester packaging 200 mg/m” Matting agent: Polymethyl methacrylate (average particle size 4.Op m) 50
mg/m” alkali-treated gelatin (isoelectric point 4.9) 1.
0g/+n” Sodium fluorinated dodecylbenzenesulfonate 50 +og/m
"Bis(vinylsulfonylmethyl) ether 20 mg/m"
Note that p) (of the above coating solution) was prepared in advance to 5.4 and then applied.

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 and create an aging sample.

Both samples were exposed to light through a step 7 pneumatic nozzle and then developed using the developer and fixer shown below, and the sensitivity and surface resistivity were determined. The sensitivity (the exposure amount was set to give an optical density of 1.0 and expressed as relative sensitivity. The results are shown in Table 2.

Development processing conditions Process Temperature Time Development 34°0 15 seconds fixing
32°c, 10 seconds of water washing, room temperature
10 second developer formulation Hydroquinone 25 gl-Phenyl-4,4dimethyl-3= Pyrazolidone 0.4g Sodium Bromide 3g 5-Methylbenzotriazole 0.3 g5-Nitroindazole
0.05g diethylaminoprono 1.2
-Diol 10 g Potassium subite 0 5-Sodium sulfosalicylate 5 Sodium ethylenediaminetetraacetate Finished up to 1 with water.

The pH is 11.5 with caustic soda. Fixer formulation (Composition A) Ammonium thiosulfate (72.5w% did.

Aqueous solution) 240 mQ 7 g 6.5g g g 13.6mQ Sodium sulfite Sodium acetate, trihydrate Borate Sodium citrate, dihydrate Acetic acid (90w% aqueous solution) (Composition B) Pure water (ion exchange water) Sulfuric acid (50w % aqueous solution) Aluminum sulfate (aqueous solution with AJOs equivalent content of 8.1v%) 17 mQ 4.7 g 26.5 g When using the fixer, the above set FRA in 500 mQ of water.

set Melt in the order of B. It was finished into Q and used.

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 t per mole 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-butylacrylate acrylic acid ternary copolymer 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-malein [t=polymer alkali-treated gelatin (isoelectric point 4.9) Silver amount Formalin 40 mg/m" 50 mg/m" 20 mg/m2 2.0 g#o" 3.5 g /m2 10mg711' Compound (0) The coating solution was coated after adjusting the pH of sodium hydroxide to 6.5 in advance.As an emulsion protective film, additives were prepared in the amounts shown below, and the emulsion was coated. Multilayer coating was performed simultaneously with the liquid.

Dioctyl fluoride 7, sulfosuccinic acid varnish f 100 mg/m' Dioctyl sulfosuccinate loomg/m" Matting agent: Amorphous silica 50 mg/m" compound (
○) 30mg/1T12 5-methylbenzotriazole compound (P) 500□g
/ m2 gallic acid propyl ester 300
mg/m” styrene-maleic acid copolymer 100mg/m
m” alkali-treated gelatin (isoelectric point 4.9) 1.
0g/m” formalin lO
mg/m” 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) 1 50mQ
Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (55% w/v aqueous solution) loOmf2 potassium carbonate 50g hydroquinone 15g 1-phenyl-3-pyrazolidone 0.5gl-7enyl-5-
Mercaptotetrazole 30mg potassium hydroxide
Amount of potassium bromide to bring the pH of the solution to 10.4
4.5g (composition B) Pure water (ion-exchanged water) 3+ng diethylene glycol 50g ethylenediaminetetraacetic acid distrilam salt 5mg Acetic acid (90% aqueous solution) Q. 3m12 When using the developer, 500m of water (2 contains the above composition A, and from the results in Table 3, as in the case of the hydrazine compound of Example 2, the sample of the present invention showed less sensitivity loss due to storage over time, and the sensitivity after processing There is also little deterioration in antistatic ability.

〔Effect of the invention〕

The present invention has an antistatic layer with excellent transparency without haze, and the surface resistivity does not deteriorate over time even if a super high contrast agent such as a hydrazine compound is used. It was possible to provide a highly stable silver halide photographic material without any sensitivity.

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 dispersed and stabilized in the antistatic layer as latex containing a substituted aziridine group. (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.