JPH03166540A - Silver halide photographic sensitive material subjected to antistatic treatment - Google Patents

Abstract

PURPOSE:To prevent the deterioration of antistatic performance after processing such as development and the occurrence of cracks during storage by forming an antistatic layer using a condensation product of cyclic saccharides with epichlorohydrin as a hardening agent. CONSTITUTION:An antistatic layer made of a reaction product of an electrically conductive water-soluble polymer and hydrophobic polymer particle with a hardening agent is formed on the plastic film substrate of a silver halide photographic sensitive material and a condensation product of cyclic saccharides with epichlorohydrin is used as the hardening agent. The resulting antistatic performance is not deteriorated even after processing and a hydrophilic colloidal layer formed on the antistatic layer does not crack. When an ultrahigh-contrast emulsion is applied to the antistatic layer, a silver halide photographic sensitive material having high stability and not causing desensitization with the lapse of time is obtd.

Description

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

[Background of the invention]

Generally, plastic film supports have strong electrostatic properties, and this often imposes many restrictions on their use. For example, supports such as polyethylene tere-7-talate are generally used in silver halide photographic materials.
It is easy to be charged especially in low humidity such as winter. Antistatic measures are especially important when high-speed photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed to light using automatic printers, as has been the case recently.

When a photosensitive material is charged, static marks appear due to the discharge, or foreign substances such as dust adhere to it, which causes bottle holes and deteriorates the quality significantly, making it extremely difficult to repair. It will be. 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, 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 a processed film is further used for printing, such as printing photosensitive materials, problems such as bottle holes 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. According to this method, it is possible to retain antistatic properties even after treatment, but this antistatic layer is coated with Haleshia.
It has been found that when a hydrophilic colloid layer such as an anti-coagulation layer is provided, cracking occurs during storage over time, greatly reducing commercial value. Furthermore, it has been found that when an ultra-high contrast emulsion using a tetrazolium compound or a hydrazine compound is applied to a plastic film support having an antistatic layer, the emulsion becomes unsightly when stored over time.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material that does not deteriorate in antistatic ability even after processing such as development, and does not crack during storage over time. Another major objective is to provide a silver halide photographic material that does not desensitize over time and is highly stable when an ultra-high contrast emulsion using a tetrazolium compound or a hydrazine compound is applied.

[Structure of the invention]

The above object of the present invention is to provide a plastic film support comprising: (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (2) an antistatic layer consisting of a reaction product of a hardening agent, wherein the hardening agent is a cyclic sugar and epichlorohydrin. This was achieved with a silver halide photographic material having an antistatic layer characterized by being a condensation product of.

The photosensitive emulsion layer preferably contains a hydrazine compound or a tetrazolium compound.

The details of the present invention will be explained below.

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

The water-soluble conductive polymer according to claim 1 of the present invention has at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carpoxyl 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 at least 5% by weight per molecule of polymer. Carpoxy 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 toooo, preferably 3500 to soooo.

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

A-1 Homopolymer A-2 Homopolymer A-3 A-4 ) 3Na A-5 S03Na A-6 So 3Na A-7 A-8 SO. Na A-9 A-11 A-12 SO. Na A-13 CH, - A-14 CHxOS03N&A-15 A-17 A-19 A-20 A-21 A-22 A-23 Dextran sal 7-eight substitution degree 2.0 Mn=100,000 A-24 A- 25 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-41 A-42 A -43 SO. Na x:y:z-80:10:10 Mu″q10,000A-44 A-45 A-46 x:y:z:w-40:30=20:10Mn匈50,000A-47 A-48 A -49 A-50 In (1) to (50) above, x, 7, z, and W each represent mol% of the monomer component, and Mn represents the average molecular weight (
In this book, the average molecular weight refers to the number average molecular weight.

) represents.

These polymers can be synthesized by polymerizing heptanomers that are commercially available or obtained by conventional methods. The amount of these compounds added is preferably 0.01 g to 10 g/1, particularly preferably 0.1 g to 5 g/1.

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 may be any combination of styrene, styrene 11 conductor, alkyl acrylate, alkyl methacrylate, ole7yne derivative, halogenated ethylene derivative, acrylamide derivative, methacrylamide derivative, vinyl ester derivative, acrylonitrile, etc. Obtained by polymerizing selected heptanomers. 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 latex from a hydrophobic polymer: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent and finely dispersing it, followed by distilling off the solvent. 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, and 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 should 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 7 B 8 B-10 B-12 B-13 COOCH. COOCIHsOH COOH B-14 CI. B-15 CN COOC+Hs n COOH
Next, the present invention is characterized in that a condensate of a hydroxyl group-containing cyclic saccharide and epichlorohydrin is used as a curing agent, and these compounds are preferably shown in the following specific examples.

(1) Condensate of inositol and epichlorohydrin C-1 C-2 8 OCR, CHCH OH C-3 HaC-4 Ha (2) Condensate of idose and epichlorohydrin C-5 CI! OH 8CH*OCHtCHCHx (3) Condensate of glucose and epichlorohydrin C-7 CHtOCHxCHCHt C-8 ＾ CHzOCHzCHCHz C-9 The hydrazine compound used in the present invention is preferably a compound represented by the following general formula [H]. be.

General formula 1"H) R.-N-N-C-R, where R. represents a l-valent organic residue, R represents a hydrogen atom or a l-valent organic residue, Q. and Q, is a hydrogen atom,
Alkylsulfonyl groups (including those with R substituents),
It represents an arylsulfonyl group (including those having a substituent), and x1 represents an oxygen atom or a sulfur atom. Among the compounds represented by the general formula (1), compounds in which %Xl is an oxygen atom and Rs is a hydrogen atom are more preferred.

The l-valent organic residues of R+ and R include aromatic residues, heterocyclic residues, and aliphatic residues.

Aromatic residues include phenyl groups, natyl groups, and substituents thereof (for example, alkyl groups, alkoxy groups, acylhydrazino groups, dialkylamino groups, alkoxy carbonyl groups, cyano groups, carboxy 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-methylphenyl group, 4-ethylphenyl group, 4-oxyethyl 7enyl group, 4-F decylphenyl group, 4-carpoxyphenyl group, 4-diethylaminophenyl group, etc. enyl group, 4-cutylaminophenyl group, 4-pendylamino 7-enyl group, 4-acetamido-2-methyl 7-enyl group, 4-(3
-ethylthioureido)7enyl group, 4-[2-(2.
4-di-tert-butyl-7enoxy)butylamide]
7-enyl group, 4-[2-(2,4-di-tert-butyl-7-enoxy)butylamido]7-enyl group, and the like.

The heterocyclic residue is a five- or six-membered monocyclic or condensed ring having at least one of oxygen, nitrogen, sulfur, and selenium, which may have a substituent. Specifically, for example, biroline ring, biridine ring, quinoline ring, indole ring, oxazole ring, penzoxazole ring, naphthoxazole ring, imidazole ring, penzimidazole ring, thiazoline ring, thiazole ring, penzothiazole ring, naphtho Examples include residues such as a thiazole ring, a selenazole ring, a penzoselenazole 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 aryl group having 6 to 18 carbon atoms such as an alkoxy group or a 7-enyl group, a halogen atom such as chloro or prom, 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 and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
18, preferably an alkyl group of 1 to 8, and specific examples include a methyl group, an ethyl group, an inbutyl group, and a l-octyl group.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, and specific examples thereof include a cycloprobyl group, a cyclohexyl group, and an adamantyl group. Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (e.g. methoxy, ethoxy, fropoxy, 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., 7-enyl group, halogen-R-substituted 7-enyl group, alkyl-substituted phenyl group), and specific examples of substituted groups include 3
-methoxyprobyl group, ethoxylponylmethyl group,
Examples include 4-chlorocyclohexyl group, penzyl group, p-methylbenzyl group, and p-chlorobenzyl group. In addition, examples of alkenyl groups include allyl (a
Examples of the lLyl) group and the alkynyl group include a globargyl 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-2 H-3 H 4 CH+ I13 H-5 H-6 H-7 H-8 H-9 H-10 H-11 H-12 H-13 H-14 H-15 H-18 H-19 H-20 H-21 CI, H-23 H-24 H-25 CH. H-28 H-29 H-30 H-31 H-32 H-33 H-34 H-35 Fl. CsH++(t) H-36 H-37 H-38 H-39 S H-40 H-41 H-42 H-43 H-44 H-45 H-46 Addition of hydrazine compound represented by general formula (H) The position is the silver halide emulsion layer and/or a non-light-sensitive layer on the silver halide emulsion layer side of the support, preferably the silver halide emulsion layer and/or a layer below it. The amount added is preferably from 10<-1> to 10<-1> mol/l mole of silver, more preferably from IO<-4> to IO<-1> mole/l 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, a substituent Rl of the 7enyl group of the tri7enyltetrazolium compound represented by the above general formula [T],
R2 and R3 are preferably hydrogen atoms or those having a negative or positive Hammett's sigma value (CaP) indicating the degree of electron attraction.

In particular, negative ones are preferred.

Hammett's sigma values for phenyl substitution have been reported in many publications, such as the Journal of Medical Chemistry (
Journal of Medical Chemistry
try) Volume 20, page 304, 1977 pm, C.
Particularly preferable groups having negative sigma values, such as those found in reports by C. Hansch et al.
value) ethyl group (-0.15), cycloprobyl group (-0
．． 21), n-probyl group (-0.13), isoprobyl group (-0.15), cyclobutyl group (-0.15)
, n-butyl group (-0.16), isO-butyl group (-
0.20), n-pentyl group (-0.15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (-0.15), hydroxyl group (-
0.37), methoxy group (-0.27), ethoxy group (
-0.24), proboxy group (-0.25), putoxy group (-0.32), pentoxy group (-0.34), etc., all of which represent the general formula (T) of the present invention. Useful as a substituent for compounds.

Specific examples of compounds 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 T-4 T-5 T-6 T-7 T-8 T-9 T-10 T-11 T-12 T-13 T-14 T-15 T-16 ↑-17 T-18 The tetrazolium compound used in the present invention is, for example, Chemical Rev
iews), Vol. 55, pp. 335-483.

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

The tetrazolium compounds used in the present invention can provide preferable properties when used alone, but the preferable properties will not deteriorate even when a plurality of them are combined in any ratio.

One preferred embodiment of the present invention is to add the tetrazolium compound according to the present invention to a silver halide emulsion layer. In another preferred embodiment of the invention, it is added to a hydrophilic colloid layer directly adjacent to the silver halide emulsion layer, or to a hydrophilic colloid layer adjacent via an intermediate layer.

In another embodiment, the tetrazolium compound according to the present invention is dissolved in a suitable organic solvent, for example, alcohols such as methanol and ethanol, ethers, esters, etc., and the halogen of the silver halide photographic light-sensitive material is coated by an overcoating method or the like. It may be incorporated into the silver halide photographic material by directly coating the outermost layer on the silver halide emulsion layer side.

The silver halide used in the silver halide photographic material according to the present invention preferably contains at least 50 mol% of silver chloride in any combination of silver chloride, silver chlorobromide, silver chloroiodobromide, etc. . The average grain size of silver halide grains is 0.025 to 0.
．． Those with a range of 5 μm are preferably used, and ゛ is 0.0.
5 to 0.30μ is more preferable.

The monodispersity of the silver halide grains according to the present invention is expressed by the following formula (
1), and its value is preferably adjusted to 5-60, more preferably 8-30.

The grain size of the silver halide grains according to the present invention is conveniently expressed by the edge length of the cubic grain, and the monodispersity is expressed by the value obtained by dividing the standard deviation of the grain size by the average grain size times 100.

Further, as the silver halide that can be used in the present invention, a type having a multilayer laminated structure of at least two layers can be preferably used. For example, silver chlorobromide particles may have silver chloride in the core and silver bromide in the shell, or conversely, silver bromide in the core and silver chloride in the shell. At this time, iodine can be contained in any layer within 5% by mole.

Furthermore, a mixture of at least two types of particles can also be used. For example, the main milk grains contain less than 10 mol% silver chloride and 5
Cubic, octahedral, or tabular silver chloroiodobromide grains containing iodine of mol% or less; subgrains are cubic, octahedral, or tabular grains containing iodine of 5 mol% or less and silver chloride of 50 mol% or more. It can be a mixed grain consisting of silver chloroiodobromide grains. When using a mixture of particles in this way, chemical sensitization of the main and sub particles is optional, but the sensitivity of the sub particles can be increased by refraining from chemical sensitization (sulfur sensitization or gold sensitization) compared to the main particles. The sensitivity may be lowered, or the sensitivity may be lowered by adjusting the particle size or the amount of noble metal such as rhodium doped inside. Furthermore, the inside of the sub-particle may be covered with gold, or the core/particle may be covered with gold.
The shell method may be used to change the combination of the core and shell to form a cover. The smaller the main particles and sub-particles, the better, for example 0.
It can take any value from 0.025 μm to 1.0 μm.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt in the form of particles, but it may also be added during chemical ripening or when preparing an emulsion coating solution.

The rhodium salt added to the silver halide emulsion used in the present invention may be a simple salt or a double salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.

The amount of rhodium salt added can be changed freely depending on the required sensitivity and gradation, but it ranges from 10-'' mol to 1 mol of silver.
A range of θ-4 moles is particularly useful.

When using rhodium salts, other inorganic compounds such as iridium salts, platinum salts, thallium salts, cobalt salts,
Gold salt etc. may also be used together. Iridicum salts can be used preferably in the range of 101 moles to 10-' moles per mole of silver, often for the purpose of improving high-light properties.

The silver halide used in the present invention can be sensitized with various chemical sensitizers. As a sensitizer,
For example, activated gelatin, sulfur sensitizers (sodium thiosulfate, allyl thiorubamide, thiourea, allyl isothiocyanate, etc.), selenium sensitizers (N,N-dimethylselenobase, selenourea, etc.), reduction sensitizers ( (triethylenetetramine, stannous chloride, etc.), such as potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, 2-olosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc. Various noble metal sensitizers represented by can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

Further, the silver nitride emulsion used in the present invention is disclosed in, for example, U.S. Pat.
9, 3,579,345, 3,615,608, 3,598,596, 3,598,955, 3,5
92,653, No. 3,582.343, Special Publication No. 1973-
267511 40-27332, 43-13167
, 45-8833, 47-8746, and the like can be used.

Further, the silver halide emulsion used in the present invention is, for example, US Pat. No. 2.444.607, US Pat.
No. 62, No. 3.512,982, West German Application Publication No. 1,189.380, No. 2.058.626, No. 2.118.411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3.342.596, Special Publication No. 47-4417
No., West German Application Publication No. 2.149.789, Special Publication No. 3
Compounds described in No. 9-2825, Japanese Patent Publication No. 49-13566, etc., preferably, for example, 5,6-trimethylene-7-hydroxy-S-triazolo (1.5-a)
Pyrimidine, 5,6-tetramethylene-7-hydroxy-S-triazolo(1.5-a)pyrimidine, 5-methyl-7-hydroxy-S-}riazolo(1.5-a)pyrimidine, 5-methyl-7 -Hydroxy-S-triazolo(1.5-a)pyrimidine, 7-hydroxy-S-
Triazolone (1.5-a) pyrimidine, 5-methyl-
6-Bromo7-hydroxy=S-}riazolo(1.5
-a) Pyrimidines, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, probyl gallate, sodium gallate), mercaptans (1-7enyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), penzo It can be stabilized using triazoles (5-7'o muhenttriazole, 5-methylbenttriazole), benzimidazole I [(6-nitrobenzimidazole), etc.

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

The amino compounds preferably used in the present invention are primary to
Includes all quaternary amines. Examples of preferred amino compounds include alkanolamines. below,
Preferred specific examples will be listed, but the invention is not limited thereto.

diethylaminoethanoldiethylaminobutanoldiethylaminopropane-1,2-dioldimethylaminopropane-1,2-dioldiethanolaminediethylaminol-gropanoltriethanolaminediprobylaminopropane-1,2-dioldioctylamino-1-ethanoldioctylamino Propane-1,2-diolddecylaminopropane-1,2-diolddecylamino-1
-Probanol dodecylamino-1-ethanolaminopropane-1,2-diol diethylamino-2-propanol diprobanolamine glycine triethylamine triethylene diamine It may be contained in at least one layer (silver emulsion layer, protective layer, hydrophilic colloid layer of subbing layer) and/or in the developer, and a preferred embodiment is a mode in which it is contained in the developer.

The content of the amino compound varies depending on the object to be included, the type of the amino compound, etc., but a contrast promoting amount is required.

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.

The hydrophilic colloid particularly advantageously used in the present invention is gelatin, but hydrophilic colloids other than gelatin include:
For example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, such as U.S. Pat. Second
．． 525.753, acylated gelatin, phthalated gelatin, or as described in U.S. Pat. No. 2,548,520, U.S. Pat.
Examples include gelatin polymerized with polymerizable monomers having ethylene groups such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in No. 831.767. I can do it,
These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc.

Examples of the support used in the present invention include baryta paper, polyethylene coated paper, polypropylene composite, glass plate,
Typical examples include cellulose acetate, cellulose nitrate, polyester 7-ilm such as polyethylene terephthalate, polyamide 7-ilm, polyglobylene film, polycarbonate film, polystyrene 7-ilm, and the like. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

Examples of developing agents used in developing the silver halide photographic material according to the present invention include the following. HO-
(CI-CH). - Typical OH type developing agents include hydroquinone, as well as catechol, birogallol and its derivatives, ascorbic acid, chlorohydroquinone, promohydroquinone, methylhydroquinone, 2.3-dibromohydroquinone, and 2.5-diethyl. Hydroquinone, catechol, 4-
Examples include chlorocatechol, 4-7enylic acidol, 3-methoxylic acidol, 4-acetyloxyalcohol, and sodium ascorbate.

Also, I{O- (CH- CH). - Typical NH O-type developers include ortho and rose aminophenols, 4-aminophenol, 2-amino-6
-Quenylphenol, 2-amino-4-chloro~6-
Examples include 7-phenyl 7-enol, N-methyl-p-aminophenyl, and the like.

Furthermore, HIN- (CH- CH). - Examples of the NL type developer include 4-amino-2-methynole-N,N-diethynoleaniline, 2,4-diamino-N,N-diethylaniline, and N-(4-amino-3-methynolephenylene)17. Examples include luforin and p-7 enylenediamine.

Examples of the heterocyclic developer include l-7zny-3-virazolidone, l-7phenyl-4,4-dimethyl-3-virazolidone, and l-7phenyl-4-methyl-4-hydroxymethyl-3-virazolidone. - vilazolidones,
Examples include 1-7unyl-4-amino-5-virazolone and 5-aminolaucil.

Others, T. H. The Theory of the Photographic Process, 4th Edition, by James
ory of Photographic Process
ss FourthEdi tioa)# 2'91~
334 pages and Journal of the American Chemical Society.
The developer described in Erican Chemical Society, 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 12 of the developer.

Further, the developer may contain glycols as an organic solvent, and examples of such glycols include tetraethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1.4-butanediol, 1.5-pentanediol, etc. However, diethylene glycol is preferably used. The preferred amount of these glycols used is 5 to 500 g per 1Q of developer solution.
The amount is more preferably 20 to 200 g. These organic solvents can be used alone or in combination.

By developing the silver halide photographic material according to the present invention using a developer containing the above-mentioned development inhibitor, a photographic material having extremely excellent storage stability can be obtained.

The pH value of the developer having the above composition 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. As for the processing temperature, for example, the development temperature is preferably 50°C or lower, particularly preferably around 25°C to 40°C, and the developing time is generally completed within 2 minutes, particularly preferably 10 seconds to 50 seconds. often has positive 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 processes include plate development,
It may be a so-called manual development process such as frame development, or a mechanical development process 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 50W/50W to undercoated polyethylene tele7 talate
After performing a corona discharge with an energy of m"・■in, apply an antistatic liquid of the following composition to the amount of 3o■/1in.
The coating was applied using a roll-fit coating pan and an air knife at a speed of .

(Antistatic layer) Water-soluble conductive polymer 0.6 g/m as shown in Table-1 Hydrophobic polymer particles 0.4 g/+* as shown in Table-1 Hardener (C) 0.1 g/m
It was dried at 90°C for 2 minutes and heat treated at 140°C for 90 seconds.

Gelatin was applied onto this antistatic layer at a rate of 2.0 g/s' and a cracking test was conducted. Formalin and sodium 2,4-dichloro-6-hydroxy-S-}lyazine were used as hardeners for gelatin. Table 1 shows the results.
Shown below.

<Crack Test> The test piece is sealed with dry silica gel in a container with a relative humidity of approximately 0%, and stored at 40°C for 3 days. After storage, the test pieces were taken out of the container and visually ranked for the degree of cracking.

○: No cracking △: Some cracking occurs, but is acceptable for practical use a: 0 described in JP-A-55-84658 From the results in Table 1, it is clear that the samples of the present invention have an excellent effect on cracking.

Example 2 (Preparation of emulsion) A rhodium salt was prepared by a controlled double jet method in an acidic atmosphere at pH 3.0, with an average grain size of 0 to 11 IIms, a silver halide composition containing 10 lmol per mole of silver, and a monodispersity of 15. , silver chlorobromide grains containing 5 mol % of silver bromide were prepared. The elongation of the particles was carried out in a system containing 30 s+g of penzyladenine per 1% gelatin aqueous solution lI2. After mixing silver and halide, 6-methyl-4-hydroxy-1.3.3a. 7 tetrazaindene to silver halide 1
600 mg per mole was added, and then washed with water and desalted.

Then 60 arg of 6-methyl-4-hydroxy-1.3.3a,7-tetrazaindene per mole of silver halide was added followed by 15 mg per mole of silver halide.
of sodium thiosulfate was added, and sulfur sensitization was carried out at 60°C. 6-Methyl-4-hydroxy-1.3.3a. as a stabilizer after sulfur sensitization. 600 grams of 7-tetrazaindene was added per mole of silver halide.

Additives were added to the obtained emulsion in the amounts shown below, and a latex subbing treatment was performed according to Example 1 of JP-A No. 59-19941 to obtain a polyethylene tele-7 tallate support with a thickness of 100 mm. applied on the body.

Latex polymer: Styrene-butyl acrylate acrylic acid ternary copolymer polymer 1.0 g/m"Tetraphenylphosphonium chloride 30 mg/m"Saponin 200 ■guys
”Polyethylene Glyco Nore 10G Him
"Hydroquinone 200 1g/mono-styrene-maleic acid copolymer 20 g/1 hydrazine compound (shown in Table-2) 50 Him" 5-methylbenzotriazole 30 mg/s" Desensitizing dye (M) 20 B/s "Alkali-treated gelatin (isoelectric point 4.9) 1.5 g/s'
Bis(vinylsulfonylmethyl)ether 15 m
gl Ugly 3 Silver amount 2.8 g7 mouth'' (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 200 g/
s” Sodium dodecylbenzenesnolephonate lOO1g/
1 Matting agent: Polymethyl methacrylate (average particle size 3.5μ
1) 100 mg/m"Lithium nitrate 30 mg/+*'Gallic acid probyl ester 300 g/12-
Mercaptobenzimidazole-sodium 5-sulfonate 30 mg/m" Alkali-treated gelatin (isoelectric point 4.9) 1.3 g/s" Colloidal silicate force 30 Og/■2 Styrene-maleic acid 11 Combined 100 ■ “gets”
Bis(vinylsulfonylmethyl)ether 15 mg
/+*” Next, 30%
After corona discharge with a power of 11 in., a poly(styrene-butyl acrylate glycidyl methacrylate) latex polymer was applied in the presence of a hexamethyleneaziridine hardener and an antistatic layer was applied as in Example 1. Coating was carried out in the same manner, and then a packing layer having the composition shown below was prepared and applied so that the amount of additives was as shown below.

(Packing layer) Latex polymer: butyl acrylate styrene copolymer 0.5 gem” styrene-maleic acid copolymer 100 1 g/1 citric acid (after coating p.
Prepared at H5.4) 40 mg/m”Sabonin
200 lIg/m" Lithium nitrate salt 30 1g/■1 Packing dye (b) (c) SO 3 Na Alkali-treated gelatin 2.0g/m" Bis(vinylsulfonylmethyl)ether 15 mg Yaichi (puffing layer protective film) Additives were prepared in the amounts shown below and were simultaneously coated on top of the packing layer.

Dioctylsulfosuccinate 200 tag/o” Matting agent: Polymethyl methacrylate (average particle size 4.0 μ-) 50 m
g/a” alkali-treated gelatin (isoelectric point 4.9) 1.0
g/m” Sodium fluorinated dodecylbenzenesulfonate
50 mg/m Mushroom Bis(vinylsulfonylmethyl) Koichitel 20 g/2 2 The pH of the above coating solution was adjusted 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 and create an aging sample. After exposing both samples to light through a step wedge, they were developed using the developer and fixer shown below, and then the sensitivity and surface resistivity were determined. Note that the sensitivity was expressed as a relative sensitivity, with the exposure amount giving an optical density of 1.0. The results are shown in Table 2.

``Man'' L Mori Jul average step Temperature Time development 34℃ 15 seconds fixing 32℃ 1O seconds Washing Room temperature 1O seconds Developer formulation Hydroquinone 25 gl-Phenyl-4,4dimethyl-3-virazolidone 0.4g Sodium bromide 3g 5-methyl Benzotriazole 0.3g5-nitroindazole
0.05g diethylaminopropane - 1.2
-Diol 10 g Potassium sulfite 90 g Sodium 5-sulfosalicylate 75 g Sodium ethylenediaminetetraacetate 2 g Finished to II2 with water.

The pH was adjusted to 11.5 with caustic soda.

Fixer prescription (Kumiai A) Ammonium thiosulfate (72.5v% aqueous solution) 240
m (1 Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g 1! acid
6g Sodium citrate dihydrate 2g Acetic acid (90w% aqueous solution) 13.6mg
(Set fRB) Pure water (ion exchange water) 17 mQ sulfur 18 (50v% aqueous solution) 4.7g [
When using 26.5 g of fixer solution, 26.5 g of acid aluminum (an aqueous solution with an AM, O. equivalent content of 8.1 v%) were dissolved in 500 ml of water (the above composition A1 group IgB was dissolved in the order of 2, finished to 1I2, and used. Table 2 From the results, it can be seen that the samples of the present invention show less sensitivity loss due to storage over time, and less deterioration of antistatic ability after processing.

Example 3 Similar to Example 2, rhodium salt was added at 1 mole of silver per mole of silver.
Silver chlorobromide grains containing 2 mol % of silver bromide with an average particle diameter of 0.20 .mu.m and a monodispersity of 20 were prepared.

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 to obtain the subbed polyethylene Tele 7 used in Example 1.
Coated on a tallate support.

Latex polymer: Styrene/butyl acrylate acrylic acid ternary copolymer polymer 1.0g/seal! 7 enol
l Ilgim”Sabonin
200 g/-3 Sodium dodecylbenzenesulfonate 50 mg/-stetrazolium compound (shown in Table 3) 50 g/s" Compound (N) Compound (0) Styrene-maleic acid copolymer Alkali-treated gelatin (etc.) Electrical point 4,9) Silver amount Formalin compound (N) 40mg/m"50mg/+a"20+mg/m" 2.0g/1 3.5g/m"10mg/m" Compound (0) The coating liquid should be prepared in advance. The sodium hydroxide solution was applied after adjusting the pH to 6.5. As an emulsion protective film, additives were prepared in the amounts shown below and were coated simultaneously with the emulsion coating solution.

Fluorinated dioctyl sulfosuccinate loo+sg/m″
Dioctinoresnorephosuccinic acid ester 100mg
/Amount 3 Matting agent: Amorphous silica 50g
/-8 compound (0) 3
0mg/Peng 25-methynolebenzotriazole
20mg/s” Compound (P)
500g/1 gallic acid probyl ester
300mg/■Ostyrene-maleic acid copolymer
100mg/m' alkali-treated gelatin (isoelectric point 4.9) 1.0g/1" formalin
101g/-8 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.

(Set A) Pure water (ion exchange water) 150mQ ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (
55% W/V aqueous solution) 100ml potassium carbonate 50g hydroquinone
15g 1-phenyl-5-mercaptotetrazole 30mg potassium hydroxide Adjust the pH of the working solution to lO. Potassium bromide amount to 4
4.5g (group B) Pure water (ion exchange water) 3tsg diethylene glycol 50g ethylenediaminetetraacetic acid disodium salt 25mg acetic acid (90% aqueous solution) 0. 3m (
2! - Phenyl-3-virazolidone 500 1 g When using the developer, prepare the above composition in 500 ml of water. From the results of Composition Table 3, it can be seen that, as in the case of the hydrazine compound of Example 2, the sensitivity of the sample of the present invention decreases due to storage over time. There is little deterioration in antistatic ability after treatment.

〔Effect of the invention〕

According to the present invention, the antistatic ability does not deteriorate even after treatment,
Moreover, when a hydrophilic colloid layer is provided as an upper layer, an antistatic layer for a plastic film support that does not cause cracking, and when this antistatic layer is applied to an ultra-high contrast emulsion, a highly stable halogenated layer that does not desensitize over time. We were able to provide a silver photographic material.

Claims (1)

[Scope of Claims] [1] A plastic film support comprising an antistatic layer comprising (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (3) a reaction product of a curing agent. 1. A silver halide photographic material having an antistatic layer, wherein the hardening agent is a condensate of a cyclic sugar and epichlorohydrin. [2] The silver halide photographic material according to claim 1, wherein the photosensitive emulsion layer contains a hydrazine compound or a tetrazolium compound.