JPH0359642A - 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 providing the antistatic layer contg. crown ether in the antistatic layer. CONSTITUTION:A plastic film formed by having the antistatic layer consisting of the reaction product of a water soluble conductive polymer, hydrophobic polymer particles and a hardener has the antistatic layer in which the water soluble conductive polymer has the crown ether in the antistatic layer. 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, plastic 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 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 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 object of the present invention is to provide a plastic film having an antistatic layer consisting of a water-soluble conductive polymer (1) hydrophobic polymer particles, (2) a reaction product of a curing agent, wherein the water-soluble conductive polymer is This is achieved by a silver halide photographic light-sensitive material characterized in that it has an antistatic layer containing a crown ether therein, and further contains a hydrazine compound or a tetrazolium compound.

The details of the present invention will be explained below.

When used alone, the water-soluble conductive polymer of the present invention can form a transparent layer, but even slight variations in drying conditions can 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 3000 to 1oooo.

and preferably 3,500 to 50,000.

Examples of the water-soluble conductive polymer used in the present invention are listed below, but are not limited to these. Homopolymer-2 Homopolymer-3 -4 )03Na -5 -6 CH.

-7- SO, Na -9 30, Na 1 I2 O3Na 2 -13 -14 -15 C.F.I.

17 9 -20 CHl x:y:z=85:10: 5 -21 -22 03Na x:y:z-80:lO:10 M=15,000^ 3 Degree of dextran sulfate substitution 2.0 M- 100,000-24 x:y:z-50:40:10 M#100,0005 6 7 8 SO, Na -29 -30 -31 -32 -33 A 4 -35 -36 -37 -38 -39 -40 H3 1 2 3 8-44 M#60,0006--48)su3Na x:y:z:w-40:30:20:10M#50,000M#30,000A-49 A-50 In addition, the above ( In 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).

These polymers can be made into synthetic leather by polymerizing commercially available or conventionally obtained 7-mer. The amount of these compounds added is preferably 0.01 g=lOg/l, particularly preferably 0.1 g to 5 g/l.

These compounds can be used alone or mixed with various hydrophilic binders or hydrophobic binders to form a layer. Particularly advantageously used as hydrophilic binders are gelatin or polyacrylamide, but others include colloidal albumin, cellulose acetate, cellulose nitrate, polyvinyl alcohol, hydrolyzed polyvinyl acetate, heptalyl Examples include gelatin. As a hydrophobic binder, the molecular weight is 2.
10,000 to 4,000,000 or more, examples include styrene-butyl acrylate-acrylic 93-element copolymer polymer, butyl acrylate-acrylonitrile-acrylic acid ternary copolymer polymer, and methyl methacrylate-ethyl acrylate-acrylic acid ternary copolymer polymer. .

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 selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene 11 conductors, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination. Tsuma o I!
obtained by combining 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. Emulsion polymerization is preferable because a complete product can be produced.

As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant.
It is preferable that the amount of 0 is less than or equal to %. 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.

-1 -3 -4 -6 B-7 - -11 -12 -13 Hl COOC on αχ! H,0H Coo)I4H3-15 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 dye may be added to give them a blue tint so as not to substantially inhibit light transmission. Also 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. The energy value of corona discharge treatment is l mW” l
Particularly preferably applied is l[lF/a''ain.

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.

Next, as specific compounds of the crown ether included in the disclosure of the present invention, the following are listed above. 17 -18 HOH -19 -20 CH, -COOH C-21 C-22 -23 -24 The hydrazine compound used in the present invention is preferably represented by the following general formula (H). It is a compound that

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

In the formula, R represents a monovalent organic residue, R1 represents a hydrogen atom or represents a monovalent organic residue, Ql and Q represent a hydrogen atom, an alkylsulfonyl group (some with substituents) include)
, arylsulfonyl group (including those with substituents)
, and xl represents an oxygen atom or a sulfur atom. Among the compounds represented by the general formula (H), compounds in which Xl is an oxygen atom and R2 is a hydrogen atom are more preferred.

The monovalent organic residues for R and Rt 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 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]
Examples include phenyl group, 4-[2-(2,4-di-tart-butylphenoxy)butyramido]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, 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. carbon number 1 to 4
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 number t
-U, preferably an alkyl group of 1 to 8, and specifically, for example, a methyl group, an ethyl group, an isobutyl group, a l-octyl group, etc.

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
-Methoxyglobyl group, ethoxycarbonylmethyl group, benzyl group, p-methylbenzyl group, p-chlorobenzyl group and the like. Examples of the alkenyl group include an allyl group, and examples of the alkynyl group include a propargyl group.

Preferred specific examples of the hydrazine compound of the present invention are shown below, but the present invention is not limited thereto in any way.

− -3 -4 -5 − H - 7 II - 8 I-9 II-10 -11 -12 -13 -14 -15 -16 H-17 H-18 )1-19 0 -21 -22 CH.

-23 -24 -25 -26 C.B.

-29 0 -31 -33 -34 -35 -37 -38 -41 -1-44 -45 -46 The hydrazine compound represented by formula (H) is added to the silver halide emulsion layer and/or the support. It is a non-photosensitive layer on the side of the silver halide emulsion layer on the body, preferably the silver halide emulsion layer and/or a layer below it. The amount added is preferably 101 to 10-' mole/1 mole of silver, more preferably lo-4 to 10-2 mole/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, substituents R, % of the phenyl group 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 (C.

Examples of groups having particularly preferable negative sigma values include methyl groups (σP=-0.171: dP values for both A) and 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), amino group (-0,66), acetylamide 7 group (-0,15), hydroxyl group (-0,37),
Methoxy group (-0,27), ethoxy group (-0,24)
, propoxy group (-0,25), butoxy group (-0,3
2), pentoxy group (-0,34)', etc.
All of these are useful as substituents for 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 compounds of the present invention are limited to these (exemplary compounds) T-1 -4 -6- 7- - 10 1 - 12 3 - 14 - 15 - 16 17 -18 The tetrazolium compound used in the present invention is described, for example, in 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 preferably used in an amount of about 1 sg to 10 g, preferably about 10 mg to 2 g, per mole of silver halide contained in the silver halide photographic 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 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,
No. 118.411, Japanese Patent Publication No. 434133, U.S. Patent No. 3,342,596, Japanese Patent Publication No. 47-4417, West German Publication No. 2.149.789, Japanese Patent Publication No. 39-28 Sho.
Compounds described in specifications or publications such as No. 25 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-8-triazolo (1,5-a) pyrimidine, 5-methyl-7-hydroxy-5-triazolo (1,5-a) pyrimidine, 5-methyl-7-hydroxy-5-triazolo (1, 5-a) Pyrimidine, 7-
Hydroxine-5-triacylon(1,5-a)pyrimidine, 5-methyl-6-promorph-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-nidropenzimitazole), 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 1 to 500 ppm, and the iron content is preferably 0.01=50 ppm, and even more preferably 0.11-1 Opp. The amount of calcium and iron can be adjusted in this way 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, furohydroquinone, methylhydroquinone, 2
．． 3-dibromono-1-hydroquinone, 2,5-diethylhydroquinone, catechol, 4-chlorocatechol, 4
-phenyl-catechol, 3-methoxy-catechol,
Examples include 4-acetyl-pyrogallol and sodium ascorbic acid.

In addition, HO (CH= CB)-NHx type developer,
Ortho and para aminophenols are typical.
Examples include 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, and N-methyl-p-aminophenyl.

Furthermore, examples of H2N-(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 heterocyclic developers include -pyrazolidones,
Examples include l-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 Asian 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 and hydrazide compounds can be used as preservatives, and in this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g, per developer i.

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 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. The processing temperature, for example, the development temperature is preferably 50°C or lower, particularly 25°C to 40'C! It is preferable that the development time is around 2 minutes, and the development time is generally completed within 2 minutes, but it is particularly preferable that the development time is 10 seconds to 50 seconds, which often brings about good effects. 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 discharging the undercoated polyethylene terephthalate, an antistatic liquid having the following composition was applied at the following amount using a roll-fit coating pan and an air knife at a speed of 33 m/sin. It was applied.

Water-soluble conductive polymer of the present invention (A) 0.6 g/m
2 Latex (B) 0.4g/m2 Crown Ether (C) 2.06g/m" Hardener (H) 0.1g/m"
It was dried for 90'0.2 minutes and heat treated for 140'0.90 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 Sl-rea 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.
After a cellophane adhesive tape was pressed onto the adhesive tape and the tape was suddenly peeled off, the residual ratio of the emulsion film to the adhesive area of the seven-layer tape was expressed as a percentage.

Treatment film test> In a processing bath, the emulsion surface of the sample was scratched in the shape of a substrate with a sharp end, and the surface was rubbed, and the residual rate of the emulsion film was expressed as a percentage. In practice, there is no problem if this percentage is 80% or more.

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) A rhodium salt containing 10-5 mol per mol of silver, an average grain size of 0.11 pm, 1 silver halide composition unit, and a rhodium salt containing 10-5 mol per mol of silver were prepared by Chondrold double jet method in an acidic atmosphere of pH 3.0. Silver chlorobromide particles having a dispersity of 15 and 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. After mixing silver and halide, 6-methyl-4-hydroxy-1,
600 mg of 3,3a,7tetrazaindene per mole of silver halide was added, followed by washing with water and desalting.

Then, after adding 60a+g of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene per mole of silver halide, 15a+g per mole of silver halide was added.
of sodium thiosulfate was added, and sulfur sensitization was carried out 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 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 I of JP-A-59-19941. .

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer polymer 1.0 gel! l”Tetraphenylphosphonium chloride 30 mg/111
"Saponin 200 mg/m"
Polyethylene glycol 100 mg/a+
"Hi)' Loki) 7 200 m
g/m” styrene-maleic acid copolymer 20 mg
/m” hydrazine compound (shown in Table-2) 59 m
g/m'5-methylbenzotriazole 30 m
g/m” desensitizing dye (M) 20
mg/+n” alkali-treated gelatin (isoelectric point 4.9)
1.5 g/m2 Bis(vinylsulfonylmethyl) ether 15 mg/m"lli amount 2.8 g/ra" (emulsion layer protective film) As an emulsion layer protective film, prepare the following amount and apply it to the emulsion. Coated in multiple layers at the same time.

Fluorinated dioctyl sulfosuccinate ester 200mg/
m” Sodium dodecylbenzenesulfonate 100a+g/
m” Matting agent: polymethyl methacrylate (average particle size 3°5,
u a+) 100 mg/
+"Lithium nitrate salt 30 -gem
“Gallic acid propyl ester 3 (10mg/la
"Sodium 2-mercagutobennymidazole-5-sulfonate 30 1g/rs" Alkali-treated gelatin (isoelectric point 4.9) 1.3 gem
“Colloidal silica 30 mg/m
"Styrene-maleic acid copolymer 100 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/m”min, poly(styrene-butyl acrylate-glycidyl methacrylate) latex polymer was applied in the presence of hexamethylene aziridine hardener, and an antistatic layer was further applied in Example-1.
Then, a backing layer having the composition shown below was prepared and applied in the following amounts.

(Backing layer) Latex polymer: Butyl acrylate-styrene copolymer 0.5 gem"Styrene-maleic acid copolymer 100 mg/vp"ri-1-7ra
(pH 5,44 after application: 40 rays/rays)
Saponin 200 Beta”
Balaking dye (a) CI, SO, H (b) SO, Additives were prepared in the amounts shown below and were simultaneously coated on top of the glue layer.

Dioctylsulfosuccinate ester packaging 200 mg/ln” Matting agent: Polymethyl methacrylate (average particle size 4.ON+s) 50
mg/+”alkali-treated gelatin (isoelectric point 4.9) 1-
Og/m” Sodium fluorinated dodecylbenzenesulfonate 50 mg/m”
Bis(vinylsulfonylmethyl) ether 20 g/l 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 556c 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.

4444 Rainbow process Temperature Time development 34°C 15 seconds fixing 32°C 10 seconds washing with water Room temperature 10 seconds Developer formulation Hydroquinone 25 gl-Phenyl-4,4dimethyl-3-pyrazolidone 0.4g Sodium bromide 3g 5-methylbenzotriazole 0. 3g5-nitroindazole
0.05g diethylaminoglobin-1,2-diol 0g potassium sulfite 0 sodium 5-sulfosalicylate 5 Sodium ethylenediaminetetraacetate Finished to IQ with water.

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

Aqueous solution) 240 ra (1 7g 6.5g g g 13.6m (2 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 (AM, O, converted content is 8.1w%)
aqueous solution) 17 mα 4.7 g 26.5 g When using the fixer, the above groups t and A are mixed in 500 m<2 of water.

set Melt in the order of B. It was finished to 112 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, a salt odor containing rhodium salt in an amount of 1 O -1 mol per mol of silver, an average particle size of 0.20 μm, and 2 mol % of silver bromide with a monodispersity of 20 was prepared. Silver oxide 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-butyl acrylate acrylic acid ternary copolymer polymer 1.0g/m”phenol
l mg/*”saponin
2001g/Sodium Dodecylbenzenesulfonate 50s+g/m”
Tetrazolium compound (shown in Table-3) 50mg/+
"Compound (N) Compound (0) Styrene-maleic acid copolymer alkali-treated gelatin (isoelectric point 4.9) Silver amount formalin 40 g71 50 mg/m" 20 g/1 2, Og/m" 3. 5g/m"10mg/m" 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 ester i00 g/l dioctyl sulfosuccinate matting agent: amorphous silica 50 gets
"Compound (0) 30mg
/m”5-methylbenzotriazole 20a
+g/m” Compound (P) 5
00 sog/m” gallic acid propyl ester 3
00sg/m” styrene-maleic acid copolymer
100mg/s” alkali-treated gelatin (isoelectric point 4.9
) 1. Og/m” formalin
1Omg/m” In addition, adjust the pH with citric acid in advance.
It was applied after adjusting to 5.4.

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

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-exchanged water) 150a Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g Potassium sulfite (55% w/v aqueous solution) 100a Potassium carbonate
50g hydroquinone
15gl-phenyl-5-mercaptotetrazole 30mg potassium hydroxide Adjust the pH of the working solution to IO. Potassium bromide amount to 4
4.5g (composition) Pure water (ion-exchanged water) 3mg diethylene glycol ethylenediaminetetraacetic acid disodium salt Acetic acid (90% aqueous solution) 0g 25g 0,3sffi l-phenyl-3-pyrazolidone 500a+g Water 500a+4 when using developer The above set fRA is inside.

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

〔Effect 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 and stability. It was possible to provide a silver halide photographic light-sensitive material with high silver halide content.

Claims (2)

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