JPH03219239A - Silver halide photographic sensitive material subjected to antistatic treatment - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which maintains high antistatic performance and has excellent pressure resistance by providing an antistatic layer consisting of a water-soluble conductive polymer, the reaction product of a hardener and a specific water-soluble polymer on at least one side of a substrate. CONSTITUTION:The antistatic layer consisting of the water-soluble conductive polymer, the reaction product of the hardener and the specific water-soluble polymer expressed by formula I is provided on at least one side of the substrate. In the formula I, R1 and R2 respectively denote a hydrogen atom, alkyl group, halogen atom, etc.; L denotes a -CONH-, etc.; J denotes an alkylene group, arylene group, etc. Q denotes a hydrogen atom, 1 to 20C alkylene group, etc.; Y denotes a hydrogen atom or (L)p(J)qQ. The silver halide photographic sensitive material having the excellent pressure resistance and the high antistatic performance is obtd. in this way.

Description

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

[Background of the invention]

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

When a photosensitive material is charged, static marks appear due to the discharge, or foreign matter such as dust adheres to it, which causes pinholes and significantly degrades the quality, making it extremely difficult to repair. I'll put it down. For this reason, antistatic agents are generally used in photosensitive materials, and recently, fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, and sulfonic acid Alternatively, a polymer having a phosphoric acid group in the molecule is used.

In particular, adjusting the charge series using fluorosurfactants or improving conductivity using conductive polymers has been widely used, for example, JP-A-49-91165 and JP-A-49-91-
No. 121523 discloses an example in which an ionic polymer having a dissociative group in the polymer main chain is applied.

However, in these conventional techniques, the antistatic ability is significantly deteriorated by the development process.

This is thought to be because the antistatic ability is lost through processes such as a developing process using an alkali, an acidic fixing process, and washing with water. Therefore, when a processed film is further used for glycidation, such as in the case of printed 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. According to this method, antistatic ability can remain even after treatment, but when a hydrophilic colloid layer such as an antihalation layer is provided on this antistatic layer, the core layer becomes hard as a film. For this reason, the undercoat latex adjacent to the core layer has poor compatibility with the hydrophilic colloid layer that constitutes the emulsion layer, adhesive layer, or backing layer, resulting in film peeling and cracking during storage over time, and when the film is handled normally. It has been found that the nails easily break when folded, and furthermore, due to deterioration of pressure resistance, bending causes blackening or white desensitization, which greatly reduces commercial value.

[Purpose of the invention]

In order to solve the above-mentioned problems, the purpose of the present invention is to produce a halogen with excellent pressure resistance that does not cause deterioration in antistatic ability even after processing such as development, maintains high antistatic ability, and is resistant to breakage of nails. An object of the present invention is to provide a silver oxide photographic material.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material comprising a photosensitive silver halide emulsion layer coated on at least one side of the support.
This is achieved by a silver halide photographic light-sensitive material characterized by having an antistatic layer comprising (1) a reaction product of a water-soluble conductive polymer and (2) a water-soluble polymer represented by the following general formula [W].

General Formula [W] In the formula, R and R2 may be the same or different and each represents a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, a halogen atom, or -CH2000M.

L is -CONH-1-NHCO-1-COO-1-OC
O-1-CO-1-SO2-1-NH5O, -1-5O
Represents 2NH- or -〇-.

J is an alkylene group, preferably an alkylene group having 1 to IO carbon atoms, an arylene group, an aralkylene group (including those having substituents. Examples -(-
CH, cHcH20-)-+CH2+s (m is 0,
An integer of 2 to 40, H n represents an integer of 1 to 3. ) represents.

0M CR, °represents a hydrogen atom or R5, where M represents a water atom or a cationic group, and R9 represents a carbon atom number of 1 to
4 represents an alkyl group, R,, R, R, R, and R8 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a phenyl group, an aralkyl group, and X represents an anion. and p and q each represent 0 or 1.

Y represents a hydrogen atom or ÷L+-+JkQ.

The details of the present invention will be explained below.

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

The water-soluble conductive polymer in the antistatic layer used in the present invention has a molecular weight of 1,000 to 1,000,000 and has a sulfonic acid group or its base bonded directly to an aromatic ring or a heterocyclic group or via a divalent linking group. Especially preferred is a compound with a molecular weight of 10,000 to 500,000. The polymer can be easily synthesized by polymerizing a heptamer that is commercially available or obtained by a conventional method.

The conductivity of the conductive polymer of the present invention means that the specific resistance of the surface applied alone on a polyethylene terephthalate film of 2 g/m" or more is 10IOΩ/cm (at 23°C,
20% RH) or less.

The surface of the antistatic layer of the present invention is preferably activated by corona discharge, glow discharge, ultraviolet rays, flame treatment, or the like. A particularly preferred activation treatment is a corona discharge treatment, which is preferably carried out at a rate of l my''l kw/m''min. A particularly preferable energy intensity is 0
．． The range is 1w −1w/+n2·min.

Further, it is preferable to provide an adhesive layer made of gelatin or a gelatin derivative on the antistatic layer of the present invention, and these adhesive layers may be overlaid at the same time as the antistatic layer is applied, or
Or it can be applied after drying. This adhesive layer is 70
Preferably, the heat treatment is carried out at a temperature range of .degree. C. to 200.degree. Various hardening agents can be applied to this adhesive layer, but from the viewpoint of crosslinking of the antistatic layer of the adjacent layer and crosslinking with the hydrophilic colloid layer, acrylamide-based, aldehyde-based, aziridine-based, or peptide-based hardening agents are selected. Hardeners can be selected from , epoxy, and vinyl sulfone hardeners.

The coating solution for forming the antistatic layer of the present invention is prepared by adding a curing agent to a dispersion of a previously pH-adjusted water-soluble conductive polymer mixed in pure water, and then mixing the mixture.

pH has a high curing effect depending on the type of curing agent used.
Adjust to a stable range and use.

For the purpose of strengthening the antistatic layer film, the crosslinking degree can be set to any desired degree. However, in order to obtain the desired performance, the mixing ratio of the conductive polymer and water-soluble polymer, the coating and drying conditions for the antistatic layer, the selection and amount of crosslinking agent used, etc. will affect the results, so it is important to set good conditions. preferable. By setting these conditions, a preferable degree of crosslinking of the antistatic layer after coating and drying can be determined. The degree of swelling was 25 for the sample of the present invention.
The sample was immersed in pure water at ℃ for 60 minutes, and an adapter was attached that could measure the swollen film thickness underwater. The degree of swelling can be determined by observing with an electron microscope and comparing it with the film thickness when dry. The degree of swelling can be determined by the thickness of the film swollen by immersion/thickness of the film when dry. To indirectly determine the degree of swelling,
The amount of water absorbed is determined from the weight of a sample of a certain area when drying and the weight of the sample when swollen, the volume increased by this water is determined, and the film thickness is determined from the specific gravity to determine the degree of swelling. be able to. Such a method can be applied not only to the degree of swelling of the antistatic layer but also to backing protective layers, backing layers, silver halide emulsion layers, etc. The thickness of the antistatic layer is closely related to conductivity, and as the characteristics improve with an increase in unit volume, it is better to make it thicker, but since the flexibility of the film will be impaired, it should be 0.1-100μ.
Good results can be obtained by setting the thickness within the range of 0.1 to 10 μm, particularly preferably within the range of 0.1 to 10 μm.

-1 SO, Na LJ3ha -5 -10 o3Na SO, Na -11 M Misaki 900,000 -12 22 -23 4 25 So, Na -18 -19 20 21 26 27 28 29 Tol force P -30 P -34 P ~31 -35 Incidentally, in the above P-1-P-37, !+ 3'+
Z represents the mole % of each half-mer component, and M represents the average molecular weight (in this specification, average molecular weight refers to number average molecular weight).

It should be noted that the polymers most useful in the practice of this invention generally have an average molecular weight of about 1,000 to about 1,000,000, as described above.

The amount of the conductive polymer contained in the antistatic layer of the silver halide photographic light-sensitive material of the present invention is expressed in units of m2 in terms of solid content.
It is preferable to add 0.001g to 10g per
Particularly preferred is addition of 0.05g to 5g.

When used in a conductive polymer and backing layer, backing protection or silver halide emulsion layer, the solid content is 0.
．． It is preferable to set it to 01-10g.

Next, the curing agent used in the present invention will be described.

As the curing agent used in the present invention, the following various curing agents can be used.

■Blocked isocyanate type ■Multifunctional aziridine type ■Amy cyanoacrylate ■Epoxy type containing triphenylphosphine ■Bifunctional ethylene/reoxide type and cured by electron beam or X-ray irradiation.

(1) N-methylol type (2) Metal complex containing zinc and zirconium metal (2) Silane cassilling agent (4) Carboxy activity These curing agents will be explained below.

(2) The blocked incyanate curing agent used in the present invention is not particularly limited as long as it releases incyanate upon heating, but the compounds shown below are preferably used as specific examples.

-1 ONHC0CH2CHC*l(s C0CHzCHCaHs 1-6 C,H.

-7- -5 NO-C-OCH,CHC,H.

-8 The above compound may be dissolved in water or an organic solvent such as alcohol or acetone and added as is, or it may be dispersed using a surfactant such as dodecylbenzenesulfonate or nonylphenoxyalkylene oxide. You can add it later. The preferred amount is 1” 1000mg
/s”.

(2) Next, the polyfunctional aziridine curing agent used in the present invention is represented by the following general formula.

Here R1 is a hydrogen atom, Alki with carbon number up to 20 or aryl group, hydroxy group, Halogen source represents the child; R3 is a hydrogen atom, A with up to 10 carbon atoms Represents a rukyl group.

The following are preferably used, but to these It is not limited.

■Next, a-cyanoacrylate used in the present invention The rate compound is represented by the following general formula.

[During the ceremony, R is carbon number 1 ~12 substitutions, unsubstituted al Represents a kill group.

] below, A specific example will be shown, but limited to this 0th order, Contains epoxy groups used in the present invention isn't it.

The hardening agent is There are no particular restrictions, but As a concrete example ■ The compounds shown below are preferably used.

Specific Example Compound 10 υ -5 4-6 -7 14 15 -9 10 11 -16 -17 18 Most of the above compounds are commercially available and can be easily obtained. The addition method may be by dissolving it in water or an organic solvent such as alcohol or acetone and adding it as is, or by dispersing it using a surfactant such as dodecylbenzene sulfinate or nonyl phenoxyalkylene oxide. It may be added from The preferred addition amount is l ” 10
0067m".

Moreover, the effect can be further enhanced by using triphenylphosphine represented by the following general formula together with the above-mentioned crosslinking agent.

[In the formula, R1-R1 represents a substituted or unsubstituted alkyl group, hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group, or alkoxy group. ] Triphenyl-7-osphosphine is not particularly limited, but as specific examples, the compounds shown below are preferably used.

Next, the bifunctional ethylene oxide compound used in the present invention is represented by the following general formula.

CH,=CH-L-CI-CH! [In the formula, L represents a substituted or unsubstituted alkylene oxide steel group. ] Specific examples will be shown below, but the invention is not limited thereto.

Specific example -1 -3 -4 -5 -6 CHz -CHCo(OCHzCHx)+0OCC)l
=cH2CH*-CHCo(OCHzCHx)eoOc
cH=cH*CH3CHtC(CH*00CCH-CH
t) sCHsCH2C-CCHxOCHzCHtOOC
CH-CHt)s7 CH2=CHC00(CHzCH20)s(CHzCH
O)x-(CHzCHxO)aOccH=cHx-1
0 CH3 CH, CI, -(CH200CC-CH2).

Incidentally, in order to cure the conventional bifunctional ethylene oxide compound, it was cross-linked by heating, but since this method has a slow reaction and insufficient cross-linking, and low efficiency, in the present invention, it is cured by electron beam or It is characterized by hardening.

The intensities of electron beams and X-rays required for curing are as follows.

Electron beam intensity: 10-”-10’KW/m” (50
KW/m" is particularly preferred.) X-ray intensity: 10-"-10'KW/+i" (3
0011/w*" is particularly preferred.) Next, specific examples of the N-methylol compound used in the present invention will be shown, but the invention is not limited thereto.

6-1 6-2 CH! OB-
3-4-5 A HOH2C-N N-CH,OH Upper Suha ■Next, specific examples of metal rust bodies containing zinc and zirconium metals used in the present invention will be shown, but they are not limited thereto. do not have.

7-1 7-2 Zn (NHs)
i(CHsCOO)z Zn(NHs)*
COs-3 (N[(a)xZnOH(Cow)i) The amount of the metal complex used is preferably lo-3 to 10' mol per mol of the conductive polymer.

Conventionally, organic crosslinking agents have been mainly used, but by using the metal complex of the present invention, crosslinking can be sufficiently performed.

(2) In the present invention, a silane coupling agent can also be used as a curing agent as described below.

-1 HtNCHxCHiNHCHzCHxCHtSl(OC
Hx)s-3 CH! = Silane coupling agent such as CI-5i (OCRs) ② In the present invention, a carboxyl group-activated curing agent is also used, for example, the following carbodiimide type curing agent.

-1 -2 Next, the water-soluble polymer used in the present invention will be explained.

In the present invention, the water-soluble polymer refers to a polymer that is soluble in water, although it does not necessarily have to have a high solubility in water.

For example, 0.05g per long filtered water at 20℃
It is sufficient that it dissolves in an amount of at least 0.1 g, preferably 0.1 g or more. It is preferable that the water-soluble polymer used has a high solubility in the developing solution or fixing solution, and it is preferable that the solubility is 0.05 g or more, and more preferably 0.5 g or more in 100 g of the developing solution. Particularly preferred are those which dissolve 1 g or more.

The water-soluble polymer of the present invention contains a repeating unit of the following general formula CW).

General formula [W] In the formula, R1 and R3 may be the same or different and each represents a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having substituents, such as methyl group, ethyl group) group, propyl group, butyl group, etc., and those with substituents, etc.), halogen atom, or -〇H2
Represents C○OM.

(-CONH-1-NHCO-1-COO-1-OC
O-1-CO-1SO, -1-NH5O, -1-5o,
Represents NH- or -〇-.

J is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those having substituents).

For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc., and those with substituents), arylene group (including those with substituents; for example, phenylene group, etc.) (such as those with substituents), aralkylene groups (including those with substituents. For example, ÷CH2CHCH20±←KaiH2-)-
=, (m is an integer of 0.2 to 40, H n is an integer of 1 to 3).

Also, Q is -CR,.

I represents a hydrogen atom or R1, where M represents a hydrogen atom or a cationic group, and R9 represents an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc., or a substituent thereto) ),
Rs, R4, Rs, R6, Ra and R8 are hydrogen atoms,
Alkyl groups having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc., or those with substituents added thereto)
, alkenyl groups (e.g. vinyl groups, aryl groups, etc. or those with substituents), phenyl groups (e.g. 7
(enyl group, methoxyphenyl group, chlorophenyl group, etc.), aralkyl group (
For example, it represents a benzyl group or a substituent thereof), X represents an anion, and p and q each represent 0 or 1.

Y represents a hydrogen atom or ÷L+-fJ-, +-Q.

The synthetic water-soluble heptamer constituting the unit represented by the general formula [W] can be copolymerized with an ethylenically unsaturated monomer. Examples of copolymerizable ethylenically unsaturated monomers include styrene, alkylstyrene, hydroxyalkylstyrene (the alkyl group preferably has 1 to 4 carbon atoms, such as methyl, ethyl, butyl, etc.), α-methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, vinyl propionate, etc.), ethylenically unsaturated monocarboxylic or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid), maleic anhydride, esters of ethylenically unsaturated molar carboxylic or dicarboxylic acids (e.g. n-butyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate), ethylenically unsaturated These include molar carboxylic acids or amides of carboxylic acids (eg, acrylamide, sodium 2-acrylamido-2-methylpropanesulfonate, N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine), and the like. The synthetic water-soluble polymer may be a homopolymer or a copolymer. The copolymer may be a copolymer with a partially hydrophobic monomer, as long as the polymer itself is water-soluble.

Note that there may be restrictions on the composition of the copolymer depending on the location and amount of addition. For example, when adding it to an emulsion layer and when adding it in a large amount, the composition should be within a range that does not interfere with the effects of the addition.

Next, specific examples of synthetic water-soluble polymers having repeating units of the general formula [W] will be illustrated, but of course they are not limited thereto. Naorikko writing -1 CH2COOH -7- -13 -8 (10,000) -10 (However, n+: nz-50 mol%: 50 mol%, thousands of average molecular weight (Mn) = about 10.000 )-15 (However, n l: n x- 75 mol%: 25 mol%
, Mn=about 20,000) 20 When using the above synthetic water-soluble polymer, it preferably has a molecular weight of 1,000 to ioo, ooo, more preferably 2,000 to 50,000.

Further, in the present invention, a hydrophobic polymer can be used in combination with the above-mentioned water-soluble polymer.

As the hydrophobic polymer, those having the following general formula are preferably used.

(General formula % Formula %)
Represents one or more types. ] x: 10-95 mol% y+5-90 mol% A includes alkyl acrylate, alkyl methacrylate, olefin derivative, halogenated ethylene derivative, acrylamide derivative, methacrylamide derivative,
Examples include vinyl ester derivatives, acrylonitrile, alkyl acrylates, alkyl methacrylates,
The olefin derivative contains at least 20 mol% or more, especially 3
It is preferable that the content is 0 mol% or more.

As the silver halide agent for the light-sensitive material used in the present invention, any commonly used silver halide can be used. Further, the grain size distribution of the silver halide grains in the photographic emulsion is arbitrary, and may be polydisperse or monodisperse.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may have a regular crystal shape such as a tetrahedron or a dodecahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape.
Alternatively, it may have a composite form of these crystal forms.

It may also consist of a mixture of particles of various crystalline forms.

Also, for example, a junction type silver halide crystal in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, a silver halide crystal grown epitaxially, (for example, silver chloride on silver bromide, (Silver iodobromide, silver iodide, etc. are grown epitaxially.) It may also be a crystal in which hexagonal or octahedral silver iodide and hexahedral silver chloride are oriented overlappingly.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area. For details, see Japanese Patent Publication No. 58-1279.
It is described in specifications such as No. 21 and No. 58-113927.

It is also possible to use a combination of internal latent image type silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2086.

The silver halide grains of the light-sensitive material used in the present invention can be prepared by a neutral method, an acidic method, an ammonia method, a forward mixing method, a back mixing method, a double jet method, a Chondrald double jet method, which are well known in the photographic field. It can be manufactured by applying a method such as a congersion method or a core/shell method.

Another form of the double jet method is the triple jet method in which soluble halogen salts of different compositions are added independently (for example, soluble silver salt, soluble bromine salt, and soluble iodide salt).
can also be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver halide is produced, ie, a so-called Chondrald double jet method, can also be used.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In addition, these silver halide grains or silver halide emulsions contain salts (soluble salts) of iridium, thallium, palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, tungsten, and platinum.
At least one of these may be contained.

Known photographic additives can be used in the silver halide photographic emulsion according to the present invention.

Examples of known photographic additives include compounds described in Research Disclosure RD-17643 (1978) and RD-18716 (1 (179)) shown in the table below.

Additives Chemical sensitizers Sensitizing dye development accelerators Antifoggants Stabilizing agents Color stain inhibitors Image stabilizers Inhibitor matt agent binder RD-17643RD-18716 Page Classification Page Classification 23 III 648- Upper right 23
1V 648 right-upper right 29 1n
648- Upper right 24 Vl
649- Bottom right
25 ■ 650 - Left - Right 25 ■ 25 ~ 26 ■ 649 right ~ 650 left 4 6 26 ~ 27 26 ~ 27 7 651 right 650 right 650 right / 1 7 ■ 650 right 8 VI 650 right 6 ■ 651 right The supports used in the silver halide photographic emulsion according to the present invention include all known ones, such as polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, styrene films, baryta paper, and synthetic polymer-coated supports. Paper, etc.

The emulsion can be coated on one or both sides of the support, and when coated on both sides, the emulsion can be applied symmetrically or asymmetrically with respect to the support.

〔Example〕

Examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below.

Example-1 Monodisperse particles of silver iodobromide containing 2.0 mol% of silver iodide with an average particle size of 0.2 μm are used as cores, and 30 mol% of silver iodide
Silver iodobromide containing
grown at pH=7-8. At pAg = 8.9, equal moles of potassium bromide and silver nitrate were added, and the average particle size was 1.15 μta (A), 0 so that the average silver iodide content became silver iodobromide particles of 2.3 moles. .63μm (B
), 0.42 μm (C) monodisperse emulsion grains were prepared. The emulsion was desalted to remove excess salts using a conventional flocculation method.

That is, the temperature was maintained at 40°C, and an aqueous solution of a formalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to cause coagulation. After removing the supernatant liquid, pure water up to 40°C was further added, an aqueous magnesium sulfate solution was added again to cause coagulation, and the supernatant liquid was removed.

Sensitizing dye■ C,H.

2H8 Next, the obtained particles (B) and (C) were chemically sensitized. That is, ammonium thiocyanate, chloroauric acid, and hypo were added to perform gold-sulfur sensitization.

Then 4-hydroxy-6-methyl 1.3,3a,7
- Add chitrazaindene, then Kl and spectral sensitizing dye ■
, (■), 300 mg and 5 mg/1 mol of AgX were added, respectively, and spectral sensitization was performed.

Regarding particles A, chemical sensitization was performed using the following method.

Spectral sensitizing dyes ■ and ■, 350 mg and 10 g each
After adding and mixing 1 mol of /Agx, ammonium thiocyanate, chloroauric acid and hypo were added to perform gold-sulfuric acid sensitization. Then, 4-hydroxy-6-methyl-1°3.3
a, 7-chitrazaindene was added for stabilization.

Next, three types of emulsion grains (A), (B), and (C) were mixed at a ratio of 10%, 65%, and 25%, respectively, and the additives and lime-treated gelatin described later were added to form an emulsion coating solution. .

The following additives were added to the emulsion layer per mole of Agx.

t-Butylcatechol 400mg polyvinylpyrrolidone (molecular weight 10000) 1.0g trimethylolpropane 0g diethylene glycol g nitrophenyl-triphenyl 7-osphonium chloro! JF 5gmg1
．． Ammonium 3-dihydroxybenzene-4-sulfonate 4mg Sodium 2-mercaptobenzimidazole-5-sulfonate
15+og11g The following compounds were added to the protective layer per 1g of gelatin.

111-dimethylol-1-bromo-1-nitromethane 0 mg Styrene-areic anhydride copolymer 2.5 g Tophenyl-5-methcaptotetrazole CsF+s O÷C
HzCHzO) r ocHzcHzOHmg CaF+ySO3 mg Polymethyl methacrylate (mantle agent') with average particle size 5μm 7rag colloidal silica (average particle size 0.013μm) 0tsg (CHO) z 40% aqueous solution 1.5
a+QHCH035% 2+aQ2.
Aqueous solution of 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 2% 10II112
Next, both sides of a 180 μm polyethylene terephthalate support were subjected to a corona discharge treatment after being biaxially stretched and set.

The latex resin cited in Synthesis Example (1) described in Example 1 of JP-A-59-18945, p. 299 was applied thereon, and then the corona discharge treatment was performed again. Further, on top of this, an antistatic liquid composed of the water-soluble conductive polymer of the present invention, a water-soluble polymer, and a curing agent, and for comparison, an antistatic liquid using the hydrophobic polymer listed in Table 1 instead of the water-soluble polymer. Both sides were coated as an antistatic layer so that the coating amount was as shown in Table 1. This antistatic layer was then subjected to corona discharge treatment.

Next, the prepared emulsion layer coating solution and the protective layer coating solution are simultaneously coated in two layers in the order of the emulsion layer and the protective layer on the antistatic layer on both sides of the support, and then dried. created a film.

The samples thus obtained are shown in Table 1.

The amount of silver per side of the unexposed film of this sample was 2.7 g/
m2, and the amount of gelatin was 3.4 g/+''.

Next, the obtained sample was subjected to a bending blackening test as described below.

(Bending blackening test) The sample was conditioned for 2 hours at a relative humidity of 40% and a temperature of 23°C, and then bent 1806 times with a radius of curvature of 4 mm.

Next, the unexposed sample was treated with XD-5R developing solution for 45 seconds using a 5RX-501 automatic processor manufactured by Konica Corporation, and the resulting sample was bent to compare the density with the blackened area. The difference (ΔD) was determined. The results are summarized in Table 1.

Next, the surface resistivity of the above sample was determined by dividing the sample into two parts: before and after the exposure/development treatment described below.

Furthermore, the above sample was exposed to standard light B described in the "New Illumination Data Book" as a light source, with an exposure time of 0.1 seconds and a temperature of 3.2 seconds.
Exposure the film to the same amount of light on both sides of the film using a non-filter at m5, and develop it in the same manner as above.

(Measurement of Surface Specific Resistivity) A test piece of the sample was sandwiched between brass electrodes with an electrode spacing of 0.14 m and a length of 10 cm, and measurement was performed for 1 minute using an insulation meter TR8651 manufactured by Takeda Riken. The sample was heated at 25°C, 20% R, H,
Time Comparison A Comparison B From the results in Table 1, it can be seen that the samples of the present invention have excellent pressure resistance.

Further, it can be seen that the sample using the antistatic layer of the present invention has an excellent antistatic effect, and the deterioration of the antistatic performance is small even after treatment.

Example-2 KBrlo, 5 g, thioether CHO (C
H2)! S(CHz)zs(CHz)go)I)0.5
wt%, add 10 cc of aqueous solution and 30 g of gelatin,
Dissolved and kept at 70°C. Add 0.88 moM/l of AgNO3 aqueous solution into this solution while stirring.

30mQ, Kl and KBr (molar ratio 3.5:96.
5) Aqueous solution 0.88moQ/Q, 30vaQ
was added by double jet method. After the addition of the mixed solution was completed, the temperature was lowered to 40° C. and the pl was set to 6.0.

Thereafter, desalting and chemical sensitization were carried out in the same manner as in Example 1 to obtain a tabular silver iodobromide emulsion. Next, using this emulsion, Example-1
A silver halide photographic film was prepared in the same manner as above.

Next, a pressure blackening test was conducted in the same manner as in Example-1.

An adhesion test was also conducted as shown below. Table 2 shows the results.
Shown below.

The structural formula of the hydrophobic polymer used is as follows.

L, -1 -4 From the results in Table 2, it can be seen that the samples of the present invention have excellent pressure resistance. It can also be seen that the film adhesion properties are also improved.

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

Example 3 In the same manner as in Example 1, an emulsion coating solution and a protective layer coating solution were prepared.

Next, in the same manner as in Example 1, the emulsion coating solution and the protective layer coating solution were coated in the same multilayer manner on one side of the support coated with antistatic layers on both sides.

Next, a backing layer coating solution having the following composition was prepared.

<Backing layer> (Backing lower layer liquid) Lime-treated gelatin 70g acid-treated gelatin 5g trimethylolpropane per coating solution N2
1.5g backing dye A (see below) 1
．． 0g backing dye B (see below) 1. Og(
Backing upper layer liquid) 70g lime-treated gelatin per 11 coating liquids 5g trimethylolpropane
1.5g backing dye A 1
．． Og backing dye B 1. OgK
NOs O-5gC,,
Hz+C0NH(CHzCf(20), H1,5gC,
H.

Backing dye B C,H.

Fth Cs0 (CHiCHzO) 1°CI(, CH20
H0,1g 1.3.5- 2% aqueous solution of triazine sodium salt 5
mQ: 1.1 g of polymethyl methacrylate particles having an area average particle size of 3.5 μl Next, the backing layer was simultaneously coated in multiple layers on the support coated with the antistatic layer on the side opposite to the emulsion layer.

Regarding the sample obtained as described above, the bending blackening performance and charging performance were evaluated in the same manner as in Example-I. The evaluation is shown in Table 3.

Baking Dye A From the results in Table 3, it can be seen that the samples of the present invention have excellent pressure resistance. Furthermore, it can be seen that the deterioration of the antistatic agent is small even after the development process.

[Effect on invention]

According to the present invention, it was possible to provide a silver halide photographic material having excellent pressure resistance and high antistatic performance.

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a support and a light-sensitive silver halide emulsion layer coated on at least one side,
On at least one side of the support, (1) a water-soluble conductive polymer (2) a reaction product of a curing agent and (3) the following general formula [
A silver halide photographic material comprising an antistatic layer made of a water-soluble polymer represented by W. General formula [W] ▲ Numerical formulas, chemical formulas, tables, etc.
~4 alkyl group, halogen atom, or -CH_2CO
Represents OM. L is -CONH-, -NHCO-, -COO-, -OC
O-, -CO-, -SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2NH- or -O-. J is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, an arylene group, an aralkylene group (including those having a substituent; for example, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or +■CH_2
CH_2O■_m■CH_2■_n▲There are mathematical formulas, chemical formulas, tables, etc.▼ (m is 0, an integer from 2 to 40, n is an integer from 1 to 3). Q also includes ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -OM, -NH_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , ▲There are mathematical formulas, chemical formulas, tables, etc.▼, hydrogen atom or R
_3, where M represents a hydrogen atom or a cationic group, R_9 represents an alkyl group having 1 to 4 carbon atoms, and R
_3, R_4, R_5, R_6, R_7 and R_8 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a phenyl group, an aralkyl group, X represents an anion, and p and q are each 0 Or represents 1. Y represents a hydrogen atom or ■L■_p■J■_qQ. ]