JPH0353241A - Silver halide photographic sensitive material subjected to antistatic treatment - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material having excellent adhesiveness and high stability by providing an antistatic layer consisting of a eater soluble conductive polymer which contains a specific copolymer. CONSTITUTION:The antistatic layer consisting of the reaction product of the water soluble conductive polymer, hydrophobic polymer particles and the hardener is provided. The antistatic layer in which the above-mentioned water soluble conductive polymer has the copolymer of a monomer having a sulfonic group in a residual aliphat. group and a nomomer having a reaction group having no carboxyl group is provided. The photosensitive material contains a hydrazine compd. or tetrazolium compd. consequently, the silver halide photographic sensitive material having the antistatic layer for plastic films having the high adhesiveness and the 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 Tele 7 grade are commonly 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 antistatic agents have been used, such as fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, sulfonic acids, Polymers having phosphoric acid groups in their molecules are 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 main chain of the polymer 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 the processed 7-ilm is further used for printing, such as with printing photosensitive materials, problems such as the formation of pinholes due to adhesion of dust occur.

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 photographic film having an antistatic layer for 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 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, and (2) a reaction product of a curing agent, in which the water-soluble conductive polymer is aliphatic. It has an antistatic layer comprising a copolymer of a monomer having a sulfonic acid group in its residue and a heptanomer having a reactive group not containing a carboxyl group, and the photosensitive abrasive further contains a hydrazine compound or a tetrazolium compound. This is achieved by a silver halide photographic material characterized by the following.

The details of the present invention will be explained below.

The water-soluble polymer used in the present invention is a polymer having a copolymer of a monomer having a sulfonic acid group in an aliphatic residue and a heptanomer having a reactive group not containing a carboxyl group.

Examples of water-soluble conductive polymer compounds used in the present invention are listed below, but are not limited to these. CQ CH, A 12 CI+, CH3 A 13 CH, C11, A-14 CH3 A 15 A-16 A-17 CH, A-18 A 19 CH, A-20 CH, A-21 A-22 A-23 CH ．． x:y=60:40 M#10,000M=15,000A -24 A-25 A-26 M#10,000A -28 In addition, in the above (1) to (28), x, y, z each represents the mole % of the monomer fraction, 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 synthesized by polymerizing heptanomers that are commercially available or obtained by conventional methods.

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 derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitriles, etc. in any combination. Obtained by polymerizing heptanomer. 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: 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 allows the production of

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.

B l B 2 B 3 B 4 B 5 B 6 B 7 B 8 C]1, CH, B 9 B 10 B-11 B-12? 113 1 I Cll■cho I cH2o1h I CI12CI1Ka COOCI+ , COOC,Hg - n COOH B 13 B - 14 CH3 {Cl, Ch s {CH2CH ten COOC4
Hs n COOH B-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. 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 corona discharge treatment has a power consumption of 1 mW-I.
KW/m''+in 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 vt% based on the crosslinking agent.

The hydrazine compound used in the present invention is preferably a compound represented by the following general formula C }i ).

General formula (H) Q, Q, X, 11 R, -N -N -C-R2 In the formula, R1 represents a l-valent organic residue, R2 represents a hydrogen atom or a l-valent organic residue, Q1 and Q2 are hydrogen atoms,
Alkylsulfonyl groups (including those with substituents),
It represents an arylsulfonyl group (including one having a substituent), and Xl represents an oxygen atom or a sulfur atom. Among the compounds represented by the general formula [H], compounds in which X is an oxygen atom and R2 is a hydrogen atom are more preferred.

The l-valent organic residues of 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, anruhydrazino groups, dialkylamino groups, alkoxy/alponyl groups, cyano groups, carpoxy groups, nitro groups, alkylthio groups, Hydroxy group, sulfonyl group, carbamoyl group, halogen atom, acylamino group, sulfonamide group,
urea group, thiourea group, etc.). Specific examples of those with substituents include 4-methyl 7-enyl group, 4-ethylphenyl group, 4-oxyethyl 7-enyl group, 4-dodecyl 7-enyl group, 4-carpoxyphenyl group, 4-diethylaminophenyl group. enyl group, 4-octylaminophenyl group, 4-bendylamino 7enyl group, 4-acetamido-2-methylphenyl group, 4-(3
-ethylthioureido)7enyl group, 4-[2-(2
．． 4-tert-butylphenoxy)butylamido]phenyl group, 4-[2-(2',4-tert
L-butylphenoquine)butylamide] phenyl group, and the like.

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

Specifically, for example, pyrroline ring, pyridine ring, quinoline ring, indole ring, oxazole ring, penzoxazole ring, naphthoxazole ring, imidazole ring, penzimidazole ring, thiazoline ring, thiazole ring, penzothiazole ring, naphtho Thiazole ring, selenazole ring,
Examples include residues such as a penzoselenazole ring and a naphthoselenazole ring.

These heterocycles have 1 to 4 carbon atoms, such as a methyl group or an ethyl group.
1 to 4 carbon atoms such as alkyl group, methquine group, ethoxy group, etc.
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 alkoxy group, a cyano group, an amino group, or the like.

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

Straight-chain and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
18, preferably 1 to 8 alkyl groups, and specific examples include methyl, ethyl, isobutyl, and 11-octyl groups.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as a cycloprobyl group, a cyclohexynyl group, and an adamantyl group. Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (e.g. methoxy, ethoxy, broboxy, butoxy, etc.), alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkylthio groups, amide groups, acyloxy groups,
ano 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
- Metkinpyl group, ethoxylponylmethyl group,
Examples of the alkenyl group include 4-chlorohexyl group, benzyl group, p-methylbenzyl group, and p-chlorobenzyl group.Alkenyl groups include, for example, allyl (a
Examples of the llyl) 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.

H-1 H-2 I1 3 H 4 H 5 H 6 H -7 H l0 H-12 H - 13 H - 14 ■1 -15 H l6 H 17 H l8 H - 19 H-20 ζ ■1 2l 1{ 22 H-23 H 24 H 25 CH, CH, H 26 H -30 OC+41'bs ■1 3l H 34 CH, H-35 H-38 H-39 S H -40 H 4l H-42 H-43 H- 44 H-45 H-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 underlying layer. The amount added is preferably 10-5 to 10-1 mol/1 mol of silver, more preferably 10-4 to 10-2 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, substituent Rl1 of the phenyl group of the triphenyltetrazolium compound represented by the above general formula (T)
R2 and R 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 value for 7-enyl substitution has been reported in many publications, such as the Journal of Medical Chemistry.
Tory (Journal of
Medical Chemistry, Vol. 20, p. 304, 1977, C. Hansch (c.H.
Examples of particularly preferable groups having a negative sigma value include the methyl group (σP = -0.17 or less, all σP values) and the ethyl group (-
0.15), cycloprobyl group (-0.21), n-propyl group (-0.13), isoprobyl group (-0.1
5), cyclobutyl group (-0.15), n-butyl f
(-0.16), isO-butyl group (-0.20), n
-pentyl group (-0.15), cyclohexyl group (-0
．． 22), amine 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
), bentoquine 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 Reviews.
) 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 10 mg to about 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.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the interior of the grain and the surface layer. The particles may be formed mainly on the surface or may be 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. 43-4133, U.S. Patent No. 3,342,596, Japanese Patent Publication No. 4417-1987, West German 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, e.g.
．． 6-trimethylene-7-hydroquine-S-triazo (1.5-a) Pyrimidine, 5,6-tetramethylene 7-hydroxy-s-triazo (1.5-a) Pyrimidine, 5-methyl-7- Hydroxy-S-triazo(l,5-a)pyrimidine, 5-methyl-7-hydroxyS-triazolo(1.5-a)pyrimidine, 7-
Hydroxine-S-triazolone (1.5-a) pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-triazo (1.5-a) pyrimidine, gallic acid ester (e.g. 1゛f isoamyl gallate, dodecyl gallate, probyl gallate, sodium gallate), mercaptans (1-7 phenyl-5-mercaptotetrazole,
2-mercaptobenzthiazole), penzotriazoles (5-prompenttriazole, 5-methynolebenttriazole), penzimidazoles (6-nitropentzimidazole), etc. .

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 penzotriazole can be contained in the emulsion. Alternatively, in order to increase the processing ability of the processing solution, the packing 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 l-500 ppm, and the iron content is preferably 0.01-50 ppm, more preferably 0.1-10 ppm. 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 the development of the silver halide photographic material according to the present invention include catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, promohydroquinone, methylhydroquinone, 2
, 3-dibromohydroquinone, 2,5-diethylhydroquinone, catechol, 4-chlorocatechol,
Examples include 4-phenylene catechol, 3-methoxyl catechol, 4-acetyl birogallol, and sodium ascorbate.

Also, HO- (CH=CH). -N}I. Typical mold developers include ortho and rose aminophenols, including 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, and N-methyl-p-aminophenol. There are Fenyl, etc.

Furthermore, 82N (CH=CH), NH! Examples of mold developers include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N1(4-amino-3-methylphenyl)17ruforine, and p-722. There are diamines, etc.

Examples of the heterocyclic developer include 3-virazolidone such as l-7enyl-3-virazolidone, ■-phenyl-4,4-dimethyl-3-virazolidone, and 1-7enyl-4-methyl-4-hydroxymethyl-3-virazolidone. vilazolidones,
Examples include phenyl-4-amino-5-pyrazolone and 5-aminolaucil.

T. H. The Theory of the Photographic Process, 4th Edition, by James James.
ic Process Fourth Edition)
pp. 291-334 and Journal of the American Chemical Society.
he American Chemical Society
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. In addition, the developer used for developing the photosensitive material according to the present invention may contain preservatives such as sodium sulfite,
Even if sulfites such as potassium sulfite are used, the effects of the present 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 IQ.

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,
Examples include 1,5-pentanediol, and 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.

The pH value of the above-described developing solution is preferably 9 to 13
However, from the viewpoint of preservation and photographic properties, the pH value is 10 to 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.
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. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these 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 Undercoated polyethylene terephthalate After di-corona discharge, an antistatic liquid with the following composition was applied at a speed of 33 m/min using a roll-fit coating pan and an air knife so that the amount was applied as shown below. Coated.

Water-soluble conductive polymer of the present invention (A) 0.6g/
m2 latex (B) 0.4g/m”
Hardener (H) 0.1 g/m'' 0 It was dried at 90°C for 2 minutes and heat treated at 140°C for 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-hydroxys-s-triazine sodium The results are shown in Table 1.

(1) Adhesion test/dry film test> Make shallow scratches on the emulsion surface of the sample with a razor in the shape of the substrate.
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> A large scratch was made on the emulsion surface of the sample in the processing bath using a sharp tip of a drill, and the surface was rubbed to indicate the remaining rate of the emulsion film as a percentage.

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

Table 1 (a) Mw as described in JP-A-55-84658 Mw = 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) A rhodium salt was prepared by a controlled double jet method in an acidic atmosphere of pH 3.0 at a concentration of 10-' per mole of silver.
Silver chlorobromide grains containing 5 mol % of silver bromide and having an average grain size of 0.11 μm and a monodispersity of silver halide composition of 15 were prepared. Particle extrusion was carried out in a system containing 30 mg of penzyladenine per 1% gelatin aqueous solution IQ. 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 60 mg of 6-methyl-4-hydroxy-1.3.3a per mole of silver halide. After addition of 7-tetrazaindene, 15111 g per mole of silver halide
of sodium thiosulfate was added and sulfur sensitized at 60°C. 6-Methyl-4-hydroxy-1.3.3a. as a stabilizer after sulfur sensitization. 600 mg of 7-tetrazaindene was added per mole of silver halide.

Additives were added to the resulting emulsion in the amounts shown below, and coated on a 100 μm thick polyethylene terephthalate support that had been latex subbed according to Example 1 of JP-A-59-19941. did.

Latex polymer: Styrene-butyl acrylate acrylic acid ternary copolymer polymer 1.0 g/m2 Tetraphenylphosphonium chloride 30 mg/m" Saponin 200 mg/m2
Polyethylene glycol 100 mg/m2
Hydroquinone 200 rag/
tn” styrene-maleic acid copolymer 20 mg/
m2 hydrazine compound (shown in Table-2) 50 mg
/m25-methylbenzotriazole 30 mg
/m2 desensitizing dye (M) 20
B/m2 alkali-treated gelatin (isoelectric point 4.9) 1.5
g/m2 bis(vinylsulfonylmethyl)ether 1
5 mg/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/
+n” Sodium totecylbenzenesnolephonate 100IIl
g/II12 Matting agent: Polymethyl methacrylate (average particle size 3.5μ
m) 100 11g/m
“Lithium nitrate salt 30 n+g/
m” gallic acid probyl ester 300 mg/
trr"2-) Sodium L-captobenzimidazole-5-sulfonate 30 Llg
/m” Alkali-treated gelatin (isoelectric point 4.9) 1.3
g/a” Colloidal Siri force 30
mg/+m” styrene-maleic acid copolymer 100
B/1 bis(vinylsulfonylmethyl)ether 15
rag/m” Next, on the support opposite to the emulsion layer, 30
After corona discharge with a power of W/m'' old n, poly(styrene-butyl acrylate glycidyl methacrylate) latex polymer was applied in the presence of hexamethyleneaziridine hardener and an antistatic layer was applied in Example- Coating was carried out in the same manner as in Example 1, and then a packing layer of the following composition was prepared and coated so that the additives were added in the amounts shown below.

(Packing layer) Latex polymer: Butyl acrylate styrene copolymer 0.5 g/m" Styrene-maleic acid copolymer 100 mg/m2 Citric acid (adjusted to pH 5.4 after application) 40 rag/aa2 Savonin 200 mg /+"Lithium nitrate salt 30 mg/m' Hacking dye (a) CH2So,H (b) So,K So3K (c) SO3Na Alkali-treated gelatin 2.0g/m2 Bis(vinylsulfonylmethyl) ether l5Illg/lI12 (Packing Layer protective film) Additives were prepared in the amounts shown below and were simultaneously coated on top of the layer.

Dioctylsulfosuccinate ester packing 200 mg/m” Matting agent: Polymethyl methacrylate (average particle size 4.0 μm) 50 m
g/m2 alkali-treated gelatin (isoelectric point 4.9)1. O
K/m” Fluorinated Sodium Totecylbenzenesulfonate 50I, lg/.l
l2bis(vinylsulfonylmethyl) ether 20 mg/m”
Incidentally, the pi{ of the above coating liquid was adjusted in advance to 5.4 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 to undergo forced deterioration to create an aging sample.

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

Development processing conditions Process Temperature Time Development@34°C 15 seconds fixing 32°C 10 seconds washing
Room temperature 10 seconds developer formulation Hydroquinone 25 gl-7
Enyl-41 dimethyl-3-virazolidone 0.4 g Sodium bromide 3 g 5-methylbenzotriazole 0,3 g 5-nitroindazole
0.05g diethylamine propane-1,2-
Diol 10 g Potassium sulfite 90 g Sodium 5-sulfosalicylate 75 g Sodium ethylenediaminetetraacetate Finished to 1Q with aqueous solution.

The pH is 11.5 with caustic powder. Fixer formulation (Composition A) Ammonium thiosulfate (72.5v% Shitko.

Aqueous solution) 240 m (1 17 g 6.5 g 6 g 2 g 13.6 mQ 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 (Al22On equivalent content is 8.1v)
% aqueous solution) 2 g 17 mQ 4.7 g 26.5 g When using a fixer, the above-mentioned A1 and B were dissolved in 500 ml of water in the order of 1 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, a salt odor containing 10-6 mol of rhodium salt per mol of silver, 2 mol% of silver bromide with an average particle size of 0.20 IIm and 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 resulting emulsion in the amounts shown below, and the mixture was coated on the undercoated polyethylene terephthalate support used in Example 2.

Latex polymer: Styrene-butyl acrylate acrylic acid ternary copolymer polymer LOg/m”phenol
Type I g/va 2 saponin
200mg/m"Sodium dodecylbenzenesnolephonate 50mg7m"
Tetrazolium compound (shown in Table 3) 50mg/I
II'' Compound (N) Compound (0) Styrene-maleic acid copolymer alkali-treated gelatin (isoelectric point 4.9) Silver content Formalin 40 mg/m" 50 mg/m x 20 mg/m" 2.0 g/m "3.5g/rn2 10Illg/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. Then, simultaneous multilayer coating was carried out together with the emulsion coating solution.

Fluorinated dioctyl sulfosuccinate 100 mg/m2 Dioctyl sulfosuccinate 100 mg/m2 Manoto agent: Amorphous silica 501 g/m" Compound (0) 30 mg/m
“5-Methylbenzotriazole 20mg/
m' compound (P) 500
mg/m” gallic acid brobyl ester 300
Ilg/+” styrene-maleic acid copolymer 1
00mg/m” alkali-treated gelatin (isoelectric point 4.9)
1.0g/m” formalin
10ffig/III12 The pH was adjusted to 5.4 with citric acid before coating.

Compound (P) Next, an antistatic layer and a packing 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 packing 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.

(Group A) Pure water (ion exchange water) 150n+(
2 ethylenediaminetetraacetic acid disodium salt 2 g diethylene glycol 50 g potassium sulfite (55% v/v aqueous solution) 100 mQ potassium carbonate 50 g hydroquinone 25 g l-phenyl-5-mercaptotetrazole 30 n+g potassium hydroxide Bromine in an amount to bring the pH of the working solution to 10.4 potassium
4.5g (Assembly B) Pure water (ion-exchanged water) 3mg diethylene glycol 50g ethylenediaminetetraacetic acid disodium salt 25mg acetic acid (
90% aqueous solution) 0.3tml1-
Phenyl-3-pyrazolidone 500+ng When using the developer, add 500 mQ of water to the above group FRA, and from the results in Table 3, the sample of the present invention shows little sensitivity loss due to storage over time, similar to the case of the hydrazine compound of Example 2. , there is little deterioration in 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 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 comprising a copolymer of a monomer having a sulfonic acid group in an aliphatic residue and a monomer having a reactive group not containing a carboxyl group. (2) The silver halide photographic material according to claim 1, which contains a hydrazine compound or a tetrazolium compound.