JPH0359643A - Silver halide photographic sensitive material subjected to antistatic treatment - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material which has an antistatic layer having excellent adhesiveness by having the antistatic layer in which the water soluble conductive polymer contains blocked isocyanate. CONSTITUTION:A plastic film formed by having the antistatic layer consisting of the reaction product of the water soluble conductive polymer, hydrophobic polymer particles and a hardener has the antistatic layer in which the water soluble conductive polymer contains the blocked isocyanate and further, a hydrazine compd. or tetrazolium compd. is incorporated into the photosensitive material. Thus, the silver halide photographic sensitive material which has the antistatic layer having the excellent adhesiveness, 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 [Industrial Field of Application] The present invention relates to a silver halide photographic material having an antistatic layer.

[Background of the invention]

Generally, glass films 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, but they tend to become electrically charged, especially at low humidity such as in 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 may occur due to adhesion of dust. For this reason, for example, JP-A-55-84658, JP-A-61-
No. 174542 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 processing, this antistatic layer has poor adhesion to the hydrophilic colloid layer coated on top of this layer, and the film may peel off during development. There was a drawback that it occurred.

Furthermore, when a super high contrast agent such as a hydrazine compound or a tetrazolium compound is used in a silver halide photographic light-sensitive material having such an antistatic layer, there is a problem that the material becomes desensitized over time.

[Purpose of the invention]

In order to solve the above-mentioned problems, the object of the present invention is to provide a silver halide photograph having an antistatic layer for a plastic film that does not deteriorate in antistatic ability even after processing such as development and has excellent adhesive properties. Another objective is to provide a highly stable photosensitive material that does not desensitize over time and does not change its surface resistivity even when ultrahigh contrast agents such as hydrazine compounds or tetrazolium compounds are used. An object of the present invention is to provide a silver halide photographic material.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a plastic film having an antistatic layer consisting of (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (2) a reaction product of a curing agent, in which the water-soluble conductive polymer is formed into a block. This is achieved by a silver halide photographic light-sensitive material having an antistatic layer containing an isocyanate and further containing a hydrazine compound or a tetrazolium compound.

The details of the present invention will be explained below.

The structure of the blocked isocyanate contained in the water-soluble conductive polymer used in the present invention is represented by the following general formula.

[In the formula, R1 represents a hydrogen atom or an unsubstituted or substituted alkyl group. R2 represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group, and may be combined with R1 to form a ring. ] Examples of compounds of the water-soluble conductive polymer used in the present invention are listed below, but are not limited thereto. 8 -9 -10 -11 Mn-1, 50,000 Mn = 0,500 -12 -14 -15 6 questions.

M″q25,000 −16 A-17 -18 9 C.I.

M 30,000 A-20 A-21 -22 M'+1,50,000 In the above (1) to (22), X+F+ z is the mole% of the monomer component, and M is the average molecular weight (main In the specification, average molecular weight refers to number average molecular weight.

These polymers can be made into synthetic leather by polymerizing commercially available or conventionally obtained 7-mer.

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 contains monomers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination. Obtained by polymerization. In particular, it is preferable that at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates are contained. Particularly preferred is 50 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. Once a product is produced, it is preferable to carry out emulsion polymerization at the Lira point.

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.

− − 5 10 -11 2 CH.

C00C11°C00C,H@ -n OOH -13 B -14 I3 -15 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 l IIW-I
KW/m"min 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 may be located on the opposite side of the support to the photosensitive layer, ie, on the back surface.

A preferable addition amount is 5 to 200 wt% based on the crosslinking agent.

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

General formula (H) R, -N -N -C-R.

In the formula, R represents a monovalent organic residue, R8 represents a hydrogen atom or a monovalent organic residue, Q and Q represent 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 R1 is a hydrogen atom are more preferred.

The monovalent organic residues for R and R2 include aromatic residues, heterocyclic residues, and aliphatic residues.

Aromatic residues include phenyl groups, naphthyl groups, and substituents thereof (e.g., alkyl groups, alkoxy groups, acylhydrazino groups, dialkylamino groups, alkoxycarbonyl groups, cyano groups, carboxyne groups, nitro groups, alkylthio groups, 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-oxydiethylphenyl 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-tart-butylphenoxy)butyramide]
Examples include phenyl group, 4-[2-(2,4-di-tart-butylphenoxy)butyramido-17enyl 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, to which a direct substituent may be attached.

Specifically, for example, pyrroline ring, pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, nandooxazole 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, an aryl group having 6 to 18 carbon atoms such as a phenyl group, 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, carbon atoms with 1-
18. Preferably it is an alkyl group of 1 to 8, and specific examples include a methyl group, an ethyl group, an isobutyl group, and a l-octyl group.

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
-methoxyglopyl group, ethoxycarbonylmethyl group,
Examples include 4-chlorocyclohexyl group, Hensyl group, p-methylbenzyl group, and p-chlorobenzyl group. As an alkenyl group, for example, allyl (
Examples of the allyl) group and 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 in any way.

-1 -2 -3 -4 -5 -6 C,H.

− -10 -12 3 -14 -15 -16 -17 8 9 -20 21 -22 -23 -24 -25 CH.

-26 1 27 r -28 29 -30 OC14H! # -31 -34 CH.

35 -38 9 H =40 1 -42 -43 CH.

-44 -45 -46 The hydrazine compound represented by the general formula (H) is added to the silver halide emulsion layer and/or the non-photosensitive layer on the silver halide emulsion layer side of the support, but preferably, The silver halide emulsion layer and/or its lower layer. The amount added is preferably to-' to 10-' mol/silver 1 mol,
More preferably, it is 1O-' to 1O-2 mol/1 mol 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, the phenyl group substituent R1 of the triphenyltetrazolium compound represented by the above general formula [T],
R2 and R1 are preferably hydrogen atoms or those having a negative or positive Hammett's sigma value (σP) indicating the degree of electron attraction.

In particular, negative ones are preferred.

Hammett's sigma values for phenyl substitution are found in many publications, such as the Journal of Medical Chemistry (
Journal of Medical Chemistry
try) Volume 20, page 304, 1977, C,
Hanks CC.

As a group having a particularly preferable negative sigma value, which can be seen in the ruts such as t(a n s h ),
For example, a methyl group (σP = -0..17 or less, all σP
value) ethyl group (-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), amino group (-0,66), acetylamine 7 group (-0,15), hydroxyl group (-0
, 37), methoxy group (-0,27), ethoxy group C-
0,24), propoxy group (-0,25), butoxy group (-0,32), pentoxy group (-0,34), etc., all of which are compounds of the general formula [T] of the present invention. is useful as a substituent for

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.

(Exemplary Compound) The tetrazolium compound used in the present invention is, for example, Chemical Review
s) Volume 55, pages 335-483.

The tetrazolium compound of the present invention is present in an amount of about 1 rag to 10 g, preferably about 10+*g, per mole of silver halide contained in the silver halide photographic material of the present invention.
It is preferable to use the amount up to about 2 g.

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 emulsions used in the present invention are, for example, U.S. Pat. No. 2,444.607, U.S. Pat.
No. 89.380, No. 2.058.626, No. 2.
l18.411, 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-84 liazolo
(1,5-a)pyrimidine, 5,6-tetramethylene=
7-hydroxy-5-)riazolo (1,5-a)pyrimidine, 5-methyl-7-hydroxy-3-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-8-triazolo (1 , 5-a) pyrimidine, 7-
Hydroxine-5-triacylon(1,5-a)pyrimidine, 5-methyl-6-promonohydroxy-S-
triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (1 phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), Benzotriazoles (
Stabilization is performed using 5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-nidrobenzimidazole), and the like. be able to.

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 9 ppm, more preferably 1 to 500 ppm, and the iron content is 0. O is preferably 1 to 50 ppm, more preferably 0.1 to 10 ppm. 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-chlorocatechol, 4-
Phenyl-catechol, 3-methoxy-catechol, 4
-Acetyl-pyrogallol, sodium ascorbic acid, etc.

In addition, as the HO-(C)I-CI), -NH2 type developer, ortho and rose aminophenols are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-7 There are minnow 4-chloro-6-phenylphenol, N-methyl-p-aminophenyl, and the like.

Furthermore, examples of the 82N-(C8-C1(), -NH, type developer) 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 3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-7enyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. -pyrazolidones,
Examples include 1-phenyl-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 Allerican Chemical 5o
The developer described in 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 liter of developer.

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,
Among them, diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 20 to 200 g, per developer IQ. 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.

p of the developer having the above composition (value is preferably 9 to 1)
3, but the pH value is 1O~ from the viewpoint of storage stability and photographic properties.
A range of 12 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. Regarding 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. ~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 After corona discharge was applied to subbed-treated polyethylene terephthalate, the following antistatic liquid was applied in the amount shown below using a roll-fit coating pan and an air knife at a speed of 33 m/+in. Coated.

Water-soluble conductive polymer of the present invention (A) 0.6 g/m
"Hardening agent (H) 0-1 g/m" It was dried at 90°C for 2 minutes and heat treated at 140' for 0.90 seconds.

Gelatin was coated on this antistatic layer at a concentration of 2.0 g/m'' and an adhesion test was conducted.As a hardening agent for gelatin, formalin, 2,4-dichloro-6-hydroxy s-triazine, Sodium was used.The results are shown in Table 1.

(1) Adhesion test and dry film test> On the emulsion side of the sample, use a razor to apply a pattern to the base.
The remaining rate of the emulsion film relative to the adhesive area of the cellophane tape when the cellophane adhesive tape was pressure-bonded thereon and then rapidly peeled off was expressed as a percentage.

<Test with processed film> In the processing bath, the emulsion surface of the sample was scratched in the shape of the substrate with a sharp end, and the surface was rubbed, and the residual rate of the emulsion film was expressed as a percentage.

Practically, this hundred There is no problem if the fraction is 80% or more.

(a) Described in JP-A-55-84658 Mvl=5000 SO, Na From the results in Table 1, it can be seen that the samples of the present invention have excellent adhesive properties.

Example 2 (Preparation of emulsion) Rhodium salt was prepared by Chondrold double jet method in an acidic atmosphere of pH 3.0, containing 101 mol of rhodium salt per mol of silver, average grain size of 0.11 μm, silver halide composition monodispersity. 15. Silver chlorobromide particles containing 5 mol% of silver bromide were prepared. Particle growth was carried out in a system containing 30 mg of benzyladenine per 112 1% aqueous gelatin solution. After mixing silver and halide, 6-methyl-4-hydroxy-1,
Halogenating 3, 3a, 7 tetrazaindene #! 600 mg per mole was added, and then washed with water and desalted.

Next, 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 60°C. I sensitized it with sulfur. After sulfur sensitization, 6-methyl 4-hydroxy-13,3a,7-tetrazaindene was added as a stabilizer to silver halide 1
600 grams per mole was added.

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. did.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer polymer 1.0 g/m'Tetraphenylphosphonium chloride 30 mg/San8 Saponin 20OB/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/m"5-
Methylbenzotriazole 30 mg/m” Desensitizing dye (M) 20 rag/l
Alkali-treated gelatin (isoelectric point 4.9) 1.5 gem
”Bis(vinylsulfonylmethyl)ether 15 m
g/m" Silver amount: 2.8 gem" (Emulsion layer protective film) An emulsion layer protective film was prepared in the following amount and coated simultaneously with the emulsion in a multilayer manner.

Fluorinated dioctyl sulfosuccinate ester 200mg/
+2 Sodium dodenlebenzene sulfonate 100+119
/+1” Matting agent: Polymethyl methacrylate (average particle size 3°5μ
m) 100 mg/+'
Lithium nitrate salt 30 +ag/m
"Gallic acid propyl ester 300 mg/m
"Sodium 2-mercaptobenzimidazole-5-sulfonate 30 mg/m" Alkali-treated gelatin (isoelectric point 4.9) 1.3 gem
“Colloidal silica 30 mg/+
"Styrene-maleic acid copolymer 100 mg/i"
Bis(vinylsulfonylmethyl)ether 15 mg
/m” Next, on the support opposite to the emulsion layer, 30
After corona discharge with a power of 1/1 m1n, poly(styrene-butyl acrylate-glycidyl methacrylate) latex polymer was applied in the presence of hexamethylene aziridine hardener, and an antistatic layer was further 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 ge1 styrene-maleic acid copolymer 100 mg/m" citric acid (after coating p
(prepared to H5.4) 40 mg/m”saponin
200 B/m" Baraking dye (a) (b) (c) 03Na Alkali-treated gelatin 2.0g/+w" Bis(vinylsulfonylmethyl) ether 15+mg81 (Balking layer protective film) Additives as shown below. The mixture was prepared in such a manner that the amount was adjusted to the desired amount, and was simultaneously coated in a multilayer on top of the green layer.

Dioctylsulfosuccinate ester packaging 200 mg/+m" Matting agent: Polymethyl methacrylate (average particle size 4.0 μm) 50 g/m" Alkali-treated gelatin (isoelectric point 4.9) 1-Og/m" Fluorinated Sodium dodecylbenzenesulfonate 50 mg/s+
"Bis(vinylsulfonylmethyl) ether 20 mg/a"
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. and 55% relative humidity, then sealed in a moisture-proof bag in a stacked state, and stored at 55° C. for 3 days for 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 Step Temperature Time Development 34°0 15 seconds fixing 3
2°0 10 seconds water wash Room temperature 10 seconds Developer formulation Hydroquinone 25 gl-phenyl-4,4dimethyl-3 pyrazolidone 0.4g Sodium bromide 3g 5-methylbenzotriazole 0.3g 5-nitroindazole
0.05 g Diethylaminopropane-1,2-diol 0 g Potassium sulfite 90 Sodium 5-sulfosalicylate 5 Sodium ethylenediaminetetraacetate Finished to 1I2 with water.

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

aqueous solution) 240 tsQ 7 g 6.5g g g 13.6m (i Sodium sulfite Sodium acetate, trihydrate boric acid, sodium citrate, dihydrate acetic acid (90w% aqueous solution) (Composition B) Pure water (ion exchange water) Sulfuric acid (50W% aqueous solution) Aluminum sulfate (^a, O, converted content is 8, 1% carbon dioxide aqueous solution) 17 vaQ 4.7g 26.5g When using 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, chlorobromide containing 10-' mol of rhodium salt per mol of silver and 2 mol % of silver bromide with an average particle size of 0.201 m and a monodispersity of 20 was prepared. Silver particles were created. This was treated in the same manner as in Example 2, washed with water, desalted, and then sulfur sensitized.

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-7' tyl acrylate acrylic tertiary copolymer 1.0g/m27 Enol
l
B/m"Saponin 20
0mg/+'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 compound (N) 40mg/m"50+I1g/m"20mg/m" 2. To Og 8 3-5 g/m2 10a+g/+a2 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. Coating was carried out simultaneously with the emulsion coating solution.

Fluorinated dioctyl sulfosuccinate 100 mg/m" Dioctyl sulfosuccinate 100 mg/m" Matting agent: Amorphous silica 50 mg/+" Compound (0) 30 mg/a"
5-methylbenzotriazole compound (P) 500mg
/+”Gallic acid propyl ester 300mg
/a” styrene-maleic acid copolymer 100m
g/m'alkali-treated gelatin (isoelectric point 4.9)
1. og/m” formalin
The pH was adjusted to 5.4 with citric acid in advance, and then applied.

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) 150mff
Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (55% w/v aqueous solution) 100m<2 potassium carbonate 50g hydroquinone 15g 1-7z nyl-5-mercagutotetrazole 30mg potassium hydroxide Adjust the pH of the working solution to lO. Potassium monobromide to 4
4.5g (composition B) Pure water (ion-exchanged water) 3mg diethylene glycol 50g ethylenediaminetetraacetic acid distrium salt 25mg acetic acid (9
0% aqueous solution) 0.3ml 121-phenyl-3-pyrazolidone 00mg When using a developer, add 500ml of water to 500ml+2 of water.From the results of the above composition A1 group and Table 3, the sample of the present invention is There is little deterioration in sensitivity due to storage over time, and there is little deterioration in antistatic ability after processing.

[Effects of the Invention] The present invention has an antistatic layer with excellent adhesive properties, 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. However, it was possible to provide a highly stable silver halide photographic material.

Claims (2)

[Claims] (1) In a plastic film comprising an antistatic layer comprising a reaction product of [1] a water-soluble conductive polymer, [2] hydrophobic polymer particles, and [3] a curing agent, the water-soluble conductive polymer A silver halide photographic light-sensitive material comprising an antistatic layer containing a blocked isocyanate. (2) The silver halide photographic material according to claim 1, which contains a hydrazine compound or a tetrazolium compound.