JPH03200959A - Antistatic silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve antistatic performance by forming at least one electrically conductive layer between a hydrophilic colloidal layer closest to a substrate and a layer adjacent to the colloidal layer and/or on the uppermost layer. CONSTITUTION:When an antistatic layer 1 consisting of a water soluble and electrically conductive polymer and a reaction product of hydrophobic polymer particles with a curing agent and at least one hydrophilic colloidal layer 4 are formed on at least one side of a substrate 8 to obtain a silver halide photographic sensitive material, at least one electrically conductive layer is formed between the colloidal layer 4 closest to the substrate 8 and a layer 3 adjacent to the layer 4 and/or on the uppermost layer 3. The resulting sensitive material has high resistance and can maintain antistatic performance even after processing.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material that is antistatic, and more specifically, a silver halide photographic material that has improved antistatic properties by providing a conductive layer. It relates to photosensitive materials.

[Background of the invention]

Since silver halide photographic materials generally consist of an electrically insulating support and photographic constituent layers, they are subject to contact friction or peeling from surfaces of the same or different materials during the manufacturing process and during use. Therefore, electrostatic charges tend to accumulate. The photosensitive emulsion layer is sensitized by discharging the electrostatic charges accumulated before the development process, and when the photographic film is developed, dot-like spots or dendritic or feather-like wire rings,
This results in so-called static marks. This significantly reduces the commercial value of photographic film. For example, static marks that appear on medical or industrial X-ray films can lead to very dangerous judgments, but this phenomenon becomes apparent only after the film is developed, and is one of the most troublesome problems. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the film surface or inability to apply uniformly. These static marks are becoming more likely to occur due to the increased sensitivity of photosensitive materials, high speed coating, high speed photography, high speed automatic processing, etc.

In other words, contact with various rollers, equipment, and photosensitive materials during manufacturing processes such as coating, drying, and processing and packaging of photosensitive materials, as well as during film loading, photographing, automatic processor processing, and shadow copying. There are many opportunities for friction.

Conventionally, methods for improving the electrical conductivity of photosensitive material supports and various coated surface layers include the use of hygroscopic substances, water-soluble inorganic salts,
Attempts have been made to use certain surfactants, polymers, etc.

However, many of the conventionally known antistatic agents vary depending on the type of support and the type of photographic composition.
At present, there are many cases in which the effect deteriorates or a negative effect is brought on the photographic properties, and furthermore, the antistatic property completely disappears after the development process, so that it has not been possible to obtain a completely satisfactory one. Therefore, recently, attempts have been made to improve the conductivity of photosensitive materials and provide them with antistatic properties, for example, in JP-A No. 55-84658, but while the charging properties are improved, when the photosensitive materials are wet, It has been pointed out that film peeling (the applied emulsion film peels off from the support during development processing) or scratches are likely to occur, leading to serious accidents.

Especially recently, as speeding up film transportation and processing has become mainstream, the physical properties of the film during processing are extremely important.
Needless to say, improvements in film adhesion when dry, as well as film adhesion and scratch resistance when wet, have been strongly desired.

[Purpose of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic material having improved antistatic properties without adversely affecting photographic properties.

A second object of the present invention is to provide a silver halide photographic material that has antistatic properties that do not deteriorate scratch resistance when wet during rapid processing.

A third object of the present invention is to provide a silver halide photographic material whose antistatic performance does not deteriorate even after development. Other objectives will become apparent from the description below.

[Structure of the invention]

In view of the above circumstances, the present inventor has conducted extensive studies on antistatic agents, and as a result, has found that these objects can be easily achieved by the configuration shown below, and has accomplished the present invention.

That is, on at least one side of the support, there is an antistatic layer made of a reaction product of (1) a water-soluble conductive polymer (2), hydrophobic polymer particles (3) a curing agent, and at least one In a silver halide photographic light-sensitive material having a hydrophilic colloid layer, at least one conductive layer is provided between the hydrophilic colloid layer closest to the support and the layer adjacent thereto and/or in the outermost layer. This is achieved by a silver halide photographic material characterized by having the following.

The present invention will be explained in detail below.

The present applicant has already proposed improving antistatic properties by combining various curing agents with conductive polymers and hydrophobic polymer particles for a similar purpose to the present invention, for example, in Japanese Patent Application No. 1983.
-330860, Kaihei 1-44106, etc.

However, these techniques have not yet been able to eliminate film peeling and scratches during rapid processing.

As a result of extensive studies on antistatic layers and conductive layers, the present inventors have discovered that at least one hydrophilic colloid layer is coated on a support coated with an antistatic layer on the surface, and the hydrophilic colloid layer It has been found that by forming at least one conductive layer on the far side from the support, not only the scratch resistance under rapid processing but also the adhesion of the film during drying can be significantly enhanced. .

In the present invention, the antistatic layer refers to a layer for preventing electrostatic damage initially provided on a support, and the conductive layer refers to a layer for preventing electrostatic damage provided in the constituent layers of a photosensitive material.

The functions of both layers may be essentially the same, for example (1) where the conductive layer is an antistatic layer according to the present invention.
water-soluble conductive polymer, (2) hydrophobic polymer (3)
) It may also be a layer consisting of a reaction product of a curing agent. or,
The conductive layer can be formed by using conventionally known antistatic agents such as surfactants, inorganic salts, or metal oxides alone or in combination, or by combining these with the above-mentioned (1), (2), and (3) according to the present invention.
) may be used in combination.

In the present invention, the photographic hydrophilic colloid layer and the conductive layer are at least one layer, and may be plural.

1 to 1O of the accompanying drawings are cross-sectional views showing the layer structure of the silver halide photographic material according to the present invention.

Next, (1) water-soluble conductive polymer according to the present invention will be explained.

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 hydrophobic polymer particles to prevent cracking, and the effect is significant.

Examples of the water-soluble conductive polymer of the present invention include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, and a polyethylene oxide group. . Among these groups, sulfonic acid groups, sulfuric acid ester groups, and quaternary ammonium bases are preferred. The amount of conductive groups required is 5% by weight or more per polymer molecule.

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

Next, specific examples of compounds will be given.

-5 -1 -2 So, Na -6- CHs -7 SO, Na CH * COOCH x CHs OH-4 -8 CH.

-9 P 0 -11 -12 18 =19 20 So , Na 1 SO, Na B3 M#900,000M Cape 1ull force SO, Na 5o, Na 22 -23 -24 -25 -26 P-27 -28 29 - 34 -35 -30 x:y atmosphere 60:40 M#30,000x:y:z:w=40=30:20:10x:y:z=
40=30:30 M#500,000M#300,000In the above P-1-P-37, "*V+Z is the mol% of each monomer component, and M is 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 have an average molecular weight of about 50 million to about 1 million.

The amount of the conductive polymer contained in the antistatic layer and conductive layer of the silver halide photographic light-sensitive material of the present invention is preferably 0.001 g to 10 g per unit in terms of solid content, particularly preferably 0.001 g to 10 g per unit. is to add 0.05g to 5g.

Next, (2) hydrophobic polymer particles according to the present invention will be explained.

The hydrophobic polymer particles contained in the water-soluble conductive polymer layer of (1) are contained in a so-called latex form that is substantially insoluble in water. , alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. In particular, styrene derivatives, alkyl acrylates, The alkyl methacrylate content is preferably at least 30 mol %, particularly preferably 50 mol % or more.

There are two methods to make a hydrophobic polymer into a latex form: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent, finely dispersing it, and then distilling off the solvent. Emulsion polymerization is preferable because it can produce a product.

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.

Specific examples of hydrophobic polymer particles (L-1) (L-2) (L-3) (L-4) a M-300,000 M-200,000 (L-5) (L-8) M-500,000 M-600,000 M-150,000 The conductive polymer used in the present invention has a sulfonic acid group or its base directly on the aromatic ring or heterocyclic group, or
The polymer is bonded via a valent linking group, and can be easily made into synthetic leather by polymerizing a commercially available or conventionally obtained hexamer.

In the present invention, conductivity refers to a property such that the specific resistance of the surface of a polyethylene terephthalate film applied alone at 2 g/1 or more is 10"Ω/am (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 preferable activation treatment is corona discharge treatment, and it is preferable to perform the treatment at a rate of 1 mv-1 kw/m"・win. A particularly preferable energy intensity is 0.1
The range is w −1v/sI·min.

The conductive layer coating liquid mixed with the conductive polymer, hydrophobic polymer particles, and curing agent according to the present invention is coated as an antistatic layer after subbing on a support, and can be coated with any desired coating for the purpose of strengthening the layer. The degree of crosslinking can be set. However, in order to obtain the desired performance, the mixing ratio of conductive polymer and hydrophobic polymer particles, coating and drying conditions for the layer, selection and amount of curing agent, etc. will affect the results, so it is preferable to set good conditions. .

In addition, in order to exhibit the effects of the present invention even better, a metal oxide can be used in the antistatic layer or the conductive layer. As the metal oxide, any one of indium oxide, tin oxide, or a metal oxide doped with an antimony atom or a phosphorus atom, or a combination thereof can be used.

As indium oxide, first indium oxide, (1n
20) and indium oxide (tntoi) are known, but in the present invention, it is preferable to use indium oxide (tntoi).

Further, as tin oxide, stannous oxide (SnO) and stannous oxide (SnOl) are known, but stannous oxide is preferably used in the present invention.

Specific examples of metal oxides doped with antimony atoms or phosphorus atoms include tin oxide and indium oxide. In order to dope the metal oxide with antimony or phosphorus, it is obtained by mixing a halide, alkoxide or nitrate compound of tin or indium with a halogenide, alkoxide or nitrate compound of antimony or phosphorus, and oxidizing and calcining the mixture. I can do it. These metal compounds are easily available. Further, the preferable content when doping antimony or phosphorus is 0.5 to 10% by weight relative to tin or indium. It is preferable to add these inorganic compounds by dispersing them in a hydrophilic colloid such as gelatin, or by dispersing them in a polymeric compound such as acrylic acid or maleic acid.

The loading ratio per binder is preferably 1-100% by weight.

Next, the reaction product of the curing agent (3) used for crosslinking the antistatic layer or conductive layer of the present invention includes conventionally known gelatin hardeners as curing agents.

Specific examples of curing agents particularly preferably used in the present invention are shown below, but the present invention is not limited thereto.

Hardening agent examples (A-1) (A-8) (A-2) CaO CaO (A-5) (A-6) CaO Qe (B-1) Formaldehyde CB-2) Glyoxal CB-3) Mucochloric acid, etc. Aldehyde hardener (84) Cut snow co-SO, -CB, -0-ct
t, -so, -co magazine CI (.

(B 5 ) CH2-CH5O2CI (zcHz
cIhsOz CH-CT.

(C” HzNCH1CH2NHCHHzCHzCH1
A silane coupling agent such as Si(OCHs)s(C-3)CH, CH5i(OCHs)s Next, as a preferred embodiment of the present invention, an antistatic layer is provided on a polyethylene terephthalate support coated with an undercoat layer. Layer.

This antistatic layer includes (1), (2) and (2) according to the present invention.
3), and further contains a surfactant known for boat fishing (for example, Japanese Patent Application Laid-open No. 53-21922, Japanese Patent Application Publication No. 53-21922;
No. 8-208743, No. 59-74554, No. 60-
80839, 60-94126, etc.) or inorganic compounds (e.g. NaCQ, LicQ,
Preferably, the composition may contain a combination of antistatic agents such as KNOs) and compounds described in metal oxides (e.g., JP-A No. 60-23848, JP-A No. 58-62649, JP-A No. 57-118242). , an antistatic layer having the former structure can be mentioned. Layers then applied thereon include hydrophilic colloid layers such as silver halide photographic emulsion layers, antihalation layers, interlayers or backing layers. Preferably it is a photosensitive silver halide emulsion layer or a backing layer.

A conductive layer according to the invention is then applied on top of that. The conductive layer has the same properties as the antistatic layer (1), (2), and (3).
A layer consisting of a protective layer, an intermediate layer, a silver halide photographic emulsion layer, a filter layer, etc. is formed on top of the layer.
A development control layer, an antistatic layer, an ultraviolet absorbing layer, etc. are coated, preferably a protective layer or a silver halide emulsion layer having substantially no photosensitivity.

Next is the outermost layer of the silver halide photographic light-sensitive material, which is generally completed up to the protective layer, but in the present invention, the present invention of (1), (2), and (3) The antistatic property can be further strengthened by providing a conductive layer according to the above as the outermost layer.

Note that the conductive layer includes (1), (2), and (3) according to the present invention.
The above-mentioned generally known surfactants, inorganic compounds, metal oxides, etc. may be used alone or in combination.

The term "hydrophilic colloid layer" used in the present invention refers to a hydrophilic layer provided on a silver halide photographic light-sensitive material, such as a silver halide emulsion layer containing binder components such as gelatin,
Protective layer, intermediate layer, antihalation layer, filter layer,
Refers to various layers necessary for photographic materials, such as development control layer, ultraviolet absorbing layer, undercoat layer, and backing layer.

The antistatic layer and conductive layer according to the present invention include the type and mixing ratio of the water-soluble conductive polymer (1) and the hydrophobic polymer particles (2), selection of the curing agent as a crosslinking agent, amount used, drying conditions, etc. It is preferable to set it to an optimal condition.

The degree of crosslinking caused by the curing agent can be determined from the degree of swelling. The degree of swelling is determined by immersing the sample of the present invention in pure water at 25° C. for 60 minutes, and attaching an adapter that can measure the thickness of the swollen film in water.

The degree of swelling can be determined by observing it 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, calculate the amount of water absorbed from the weight of a sample of a certain area when dry and the weight of the sample when swollen, calculate the volume increased by this water, and calculate the specific gravity. The film thickness can be calculated from the following and can be used as the degree of swelling. The preferred degree of expansion is 0.2 to 100%, more preferably 2 to 50%.

The thickness of these layers is closely related to conductivity, and as the characteristics improve with an increase in unit volume, it is better to make them thicker, but since the flexibility of the film will be impaired, it is better to make them thicker.
Good results can be obtained by setting the thickness within 100μ, particularly preferably in the range of 0.1-10μ.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be any silver halide such as silver iodobromide, silver iodochloride, silver iodochlorobromide, etc., but it is said that particularly high sensitivity can be obtained. From this point of view, silver iodobromide is preferred.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may be entirely isotropically grown like a tetrahedron, a polyhedral crystal like a sphere, a twin crystal with planar defects, or a mixed or composite type thereof. . The grain size of these silver halide grains is 0.1μ
- The particles may be as fine as the following to as large as 20 μm.

The emulsion used in the silver halide photographic material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978) pp. 22-23 1. Emulsion manufacturing method (): Hlls
ion preparation and types)
and (RD) No. 18716 (November 1979), page 648.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is described, for example, in "The theory o" by T. H. James.
f thephotographic process
"4th edition, published by Maca + 1llan (1977) 3
The method described on pages 8 to 104, "Photographic emulsion chemistry" by G. F. Dauffin, "Photographic emulsion chemistry"
ulsionChemistry 1Focal p
Published by ress (1966), Glafkides, P.
Author: “Physics and Chemistry of Photography” by Chimie etphysi
que photography”Paul M
Published by onte1 (1967), V, L, Zelik
``Manufacturing and Coating of Photographic Emulsions'' by Man et al.
and coating photography
emulsion” published by Focal press (1
964) and others.

That is, solution conditions such as neutral method, acidic method, ammonia method, etc.
It can be produced using mixing conditions such as forward mixing method, back mixing method, double jet method, Chondral double jet method, etc., particle preparation conditions such as conversion method, core/shell method, and combination methods thereof.

The grain size distribution of silver halide may be either a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

A monodisperse emulsion as used herein means that when the average particle diameter is measured by a conventional method, at least 95% of the particles in terms of number or weight are within ±40% of the average particle diameter, preferably within ±30%. It is a certain silver halide grain.

The crystal structure of silver halide may have different silver halide compositions inside and outside.

The emulsion as a preferred embodiment of the present invention is a core/shell type monodisperse emulsion having a clear two-layer structure consisting of a high iodine core portion and a low iodine shell layer.

The silver iodide content of the high iodide portion is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

Methods for producing such monodispersed emulsions are known, for example, J. Ph.
ot, Sic, pp. 12.242-251 (1963)
, JP-A-48-36890, JP-A-52-16364,
No. 55-142329, No. 58-49938, British Patent No. 1,413.748, US Patent No. 3,574.628
No. 3,655.394.

The above-mentioned monodisperse emulsion is particularly preferably an emulsion in which grains are grown by using seed crystals and supplying silver ions and/or ride ions using the seed crystals as growth nuclei.

Note that methods for obtaining core/shell emulsions include, for example, British Patent No. 1.027.146 and US Patent No. 3,505.0.
No. 68, No. 4,444.877, JP-A-60-143
This is detailed in publications such as No. 31.

The silver halide emulsion used in the present invention may be tabular grains with an aspect ratio of 5 or more.

The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness, as described in British Patent No. 2,112,157 and US Pat. No. 4,439, for example.
．． No. 520, No. 4,433.048, No. 4.414.
No. 310, No. 4,434.226, etc., and emulsion 3 can be prepared by the method described in the same publication.

The above-mentioned emulsion may be a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. . In these emulsions, cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be used in the stage of physical ripening or grain preparation. The emulsion may be subjected to water washing methods such as Nodel water washing method and flocculation sedimentation method to remove soluble salts. Preferred water washing methods include, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group as described in Japanese Patent Publication No. 35-16086, or a method using agglomerating polymer agents G 3 and G 8 as described in Japanese Patent Publication No. 63-158644. Particularly preferred desalting methods include methods using the following methods.

Various photographic additives can be used in the emulsion according to the present invention in the steps before and after physical ripening or chemical ripening. Examples of known additives include compounds described in Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 18716 (November 1979). Compound types and additives shown in these two research disclosures Chemical sensitizers Sensitizing Dye development accelerators Anticapri agents Stabilizers Color stain inhibitors Image stabilizers Ultraviolet absorbers Filters Dyes Brighteners Hardening Agent coating aid Surfactant Plasticizer Slip agent Static inhibitor Matting agent Binder - RD-17643 Page Classification 23 llI 23 IV 29 llI 24 Vl 〃 〃 25 ■ 25 ■ 25-26 ■ 〃 〃 24 V 26 Left 651 Left 650 Right 650 Right 650 Right 651 Left Supports that can be used for the photosensitive material according to the present invention include, for example, the above-mentioned RD-17643, page 28 and RD.
-18716, page 647, left column.

Suitable supports include plastic films, and the surfaces of these supports may generally be provided with an undercoat layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve adhesion of the coating layer. The emulsion according to the present invention can then be coated on one or both sides of the support thus treated.

The present invention is applicable to all silver halide photographic materials, but is particularly suitable for high-sensitivity black-and-white photographic materials.

When applying the present invention to medical X-ray radiography,
For example, a fluorescent intensifying screen whose main component is a phosphor that generates near-ultraviolet light or visible light when exposed to penetrating radiation is used. It is desirable to expose this material in close contact with both surfaces of a light-sensitive material prepared by coating both surfaces with the emulsion of the present invention.

The penetrating radiation herein refers to high-energy electromagnetic waves, and means X-rays and gamma rays.

Further, the fluorescent intensifying screen refers to, for example, an intensifying screen whose fluorescent component is mainly calcium tungstate, or a fluorescent intensifying screen whose main component is a rare earth compound activated with terbium.

〔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 grains of silver iodobromide containing 2.0 mol% of silver iodide with an average grain size of 0.2μ■ are used as nuclei, and silver iodobromide containing 30 mol% of silver iodide is heated to pH 9.3. , pAg 7.5, and then at pH 7.8 and pAg 8.9, equimolar amounts of potassium bromide and silver nitrate were added to obtain silver iodobromide grains with an average silver iodide content of 2.3 mol. Particle size 1.25μ-(A).

Monodisperse emulsion grains of 0.98 μs+ (B) and 0.60/J thick (C) 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, and an aqueous magnesium sulfate solution was added again to cause coagulation, and the supernatant liquid was removed.

Next, particles (A), (B), and (C) were treated with ammonium thiocyanate salt at 1.9×10 per mole of silver.
-3 moles, and appropriate amounts of chloroauric acid, hypo, and spectral sensitizing dyes A and B described below in a weight ratio of 200:l, total amount of 80 (1 mg) per mole of silver halide, and chemical ripening. 15 minutes before the end, 200 mg of potassium iodide was added per mole of silver, and then 4-hydroxy-
6-methyl-1,3,3a,7-chitrazaindene 3
Three types of emulsion grains were stabilized with X 10-" molar and mixed in the ratio of (A) 25%, (B) 40%, and (C) 35% in descending order of size, and the additives and lime-treated gelatin listed below were added. This was referred to as emulsion coating liquid (1).

Next, particles (B), (C), and CD') were treated in the same manner to give (B) 15%, (C) 45%, and (D) 40%.
An emulsion was prepared by mixing in the following ratio, and an emulsion coating solution (2) was prepared.

The spectral sensitizing dyes used for sample preparation are as follows.

Spectral sensitizing dye A (CHx)ssOzNa (CHx)sS(he Spectral sensitizing dye B The additives used in the emulsion solution (photosensitive silver halide coating solution) are as follows.The amount added is silver halide The amount is expressed per mole.

1.1-dimethylol-1-bromo-1-nitromethane 65+agt-butyl-catechol polyvinylpyrrolidone (molecular weight 10.000) styrene-maleic anhydride copolymer trimethylolpropane diethylene glycol nitrophenyl-triphenylphosphonium chloride 1.3-dihydroxy Ammonium benzene-4-sulfonate 2-mercaptobenzimidazole-5-sodium sulfonate 00mg 1.0g 2.5g 0g g 0mg g 1.5mg H 1-phenyl-5-mercaptotetrazole or additives used in the protective layer solution is as follows.

The amount added is shown in the amount per 112 coating liquid.

8 g of lime-treated inert gelatin, g of acid-treated gelatin, polymethyl methacrylate, matting agent with an area average particle size of 3.5 μm, silicon dioxide particles, matting agent with an area average particle size of 1.2 μm, Ludox AM (manufactured by DuPont) (colloidal silica) 2 , 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 2% aqueous solution (hardener) Glyoxal aqueous solution 40% (hardener) 1,1g 0,5g 0g 10+aQ 1,5■a C ,F,So,K
2 m gC+zl(zscONH((JlzC
HzO)sHO, 175μm thick with 5g undercoat treatment
'9 on both sides of the polyethylene terephthalate film.
After corona discharge with an energy of m /m2・min, the water-soluble conductive polymer (a) according to the present invention, the hydrophobic polymer particles (b), and the curing agent (b) were added at a weight ratio of 5
．． 5: The constituent liquid adjusted so that 3.6 = 0.9,
45m/+in so that the dry film thickness after coating is 0.7μm
It was applied uniformly to both sides using a roll-fit coating hand and an air knife at a speed of .

Thereafter, it was dried at 90°C for 2 minutes and further heat-treated at 140°C for 090 seconds to form an antistatic layer.

On the obtained film base, an emulsion layer, a protective layer, and a conductive layer were coated simultaneously on both sides at a speed of 80 m/min using two slide hopper type coaters so as to have the composition shown in Table 1, and then coated for 2 minutes. Dried in 40 seconds, sample No., (1)-No.
(42) was obtained.

In addition, the layer structure was made into the 1st layer - the 4th layer from the side near a support body.

Further, the conductive layer used in this example is as follows.

Conductive layer I: Sample No. in the table, having the same composition as the antistatic layer shown in (1), and adjusted so that the dry film thickness after coating was 0.15 μm.

Conductive layer ■: O in the front and back, same as the one shown in (3) Conductive layer ■: No in the front, same as the one shown in (5) Conductive layer ■: Gelatin and SnO with a particle size of 0.09 μm, ' The volume ratio is 55
:45, adjusted so that the dry film thickness after coating was 0.17 μm.

Conductive layer V: Same as above, ZnO with grain size of 0.11 μm.

Conductive layer ■: Borivinyl alcohol and 0.10 μm In
, 0° Curing agent for antistatic layer used in Examples -1 -8 CI HzNCHtCHzNHCToCH*CH*5
i(OCRs)s [Evaluation of antistatic performance] The antistatic performance of the obtained sample was evaluated as follows. That is, preserved samples (1) and (2) were prepared, and the surface resistivity values after preservation were measured. For measurement, the sample was placed at an electrode spacing of 0.14c.
The measurement was conducted for 1 minute using a TR8651 type insulation meter made by Takeda Riken, with the electrodes sandwiched between brass electrodes with a length of 10 cm and a length of 10 c+o.

The sample used was one that had been conditioned for 3 hours at 23° C. and 20% RH.

Storage ■: Samples were conditioned at 23°C and 148% RH for 3 hours, stacked and sealed in a moisture-proof bag, and stored at 23°C for 4 days.

Storage ■: Store the same sealed product at 40°C for 4 days. (
(forced deterioration) Also, part of the sample stored in
Using a -501 automatic developing machine (both manufactured by Konica Corp.), the developing temperature was 35°C, the fixing temperature was 32°C, and the washing water flow rate was 31°C.
The surface resistivity was also measured in the same manner as above for those subjected to development processing in the 45 second mode under the conditions of 2/win and a drying temperature of 45°C.

[Evaluation of scratch resistance]

A sample that had been conditioned for 4 hours at 23°C and 48% RH was scratched at a speed of 1cII/l1in while continuously changing the load with a 7-Ire needle with a radius of 0.3mm, and then scratched in the same manner as above. The table shows the load at which blackening begins after the development process was performed. That is, the larger the value, the better the scratch resistance.

The results obtained are shown in Table-1.

As is clear from the results in Table 1, all of the samples according to the present invention had excellent scratch resistance, lowered surface resistivity values even after forced deterioration, and had satisfactory antistatic performance. In particular, by the method shown in Emulsion 3 (Example) of JP-A No. 58-113927, tabular iodine with an average grain diameter of 1.10 Pm and an aspect ratio of 8=1 was prepared. An emulsion consisting of silver bromide grains was prepared.

The tabular silver iodobromide grains account for 80% or more of the total projected area of the grains. However, before desalting, the above-mentioned spectral sensitizing dyes A and B were added to the grains at a weight ratio of 200:1 in a total amount of 1000+ag per mole of silver halide.

When adding the spectral sensitizing dye, adjust the pH to 7.60, add phenylcarbamylated gelatin after 15 minutes, and adjust the pH with acetic acid.
was allowed to flocculate, and the supernatant was removed.

Pure water was added to the thus obtained grains so that the volume per mole of silver halide grains was 500+aff,
The spectral sensitizing dyes ■ and ■° were added in a weight ratio of 200:1 in a total amount of loOmg per mole of silver halide, and after 10 minutes, ammonium thiocyanate salt was added. 2.8X 10- per mole of silver
Chemical ripening was started by adding the appropriate amounts of chloroauric acid and hypo. After that, chemical ripening was performed for 80 minutes, and then 4-hydroxy-6-methyl-1,3,3a,7 −
Chemical ripening was completed by adding an appropriate amount of chitrazaindene.

The same additives as in Example 1 were added to the obtained emulsion,
This was designated as Emulsion Coating Solution-3. Note that the same protective layer as in Example 1 was used.

A backing layer coating solution having the following composition was also prepared.

Backing layer〉 Backing lower layer liquid〉 70g lime-treated gelatin per coating solution In 5g acid-treated gelatin 5g trimethylolpropane 1.5g Backing dye A (see below)
1. Og backing dye B (see below)
LOg (backing top layer liquid) 70 g lime-treated gelatin per 1Q coating solution Acid-treated gelatin Trimethylolpropane Backing dye A Backing dye B KNO.

CIolli +C0NH(CHtCHtO)sHg 1.5g 1.0g 1.0g 0.5g 1.5g Backing dye A Backing dye B F+*Cs0(CHzCHzO)+oCHzCHsOH
0.1 g 2% aqueous solution of 2.4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 15
taQ 1 g of polymethyl methacrylate particles with an area average particle size of 3.5 μm After coating the backing layer on one side of a film base coated with an antistatic layer on both sides in the same manner as in Example-1,
The other side has the composition shown in Table 2, an emulsion layer, a protective layer,
A conductive layer was applied and dried in the same manner as in Example-1, and sample N
o, (43) to No, (56) and comparative samples (e), (
) was obtained.

The obtained sample was evaluated for antistatic performance and scratch resistance in the same manner as in Example-1. The results obtained are shown in Table-2.

Example 3 In the same manner as in Example 2, an emulsion containing tabular silver iodobromide grains having an average grain diameter of 0.7 μm and an aspect ratio of 6:1 was prepared.

The tabular silver iodobromide grains account for 80% or more of the total projected area of the grains.

After removing excess salts from the resulting emulsion in a conventional manner, ammonium thiocyanate salt was added at a concentration of 2. OX
Chemical ripening was carried out by adding 10-'' mole and appropriate amounts of chloroauric acid and hypo.

Furthermore, 4-hydroxy-6-methyl-1,3,3a,7-
Chitrazainden 1. Added Og. After 5 minutes, sensitizing dye C shown below was added.

The amount added is 30-g per mole of silver halide.

Next, 9 g of trimethylolpropane was added to 1 mole of silver halide, 30 mg of nitrophenyllate 1nophenylphosphonium chlorite, and ammonium 1,3-dihydroxybenzene-4-sulfonate Igs.
Sodium 2-mercaptobenzimidazole-5-sulfonate lQ+ag,' 2-mercaptopenzothiazole J 10 mg, 1-phenyl-5-mercaptotetrazole υH 1,1-dimethylol-1-bromo-1-di 0 mg of tromethane was added to prepare emulsion coating liquid-4.

The protective layer had the same composition as Example-1.

As a banking layer, a backing layer solution was prepared consisting of 400 g of gelatin, 2 g of polymethyl methacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following antihalation dye, and glyoxal.

Antihalation dye Furthermore, the following additives were added to the coating solution for the backing layer.

03Na CsF+s 0 (CHxCHzO). -CI(!O
To H, 0f (C, F,, So, 2 mg 3i + g sodium chloride 50 + g matting agent 7 wags made of polymethyl methacrylate with an average particle size of 5 μm, colloidal silica 70 + sg with an average particle size of 0.013 μm, etc.) were added.

Furthermore, 2,4-dichloro-6-hydroxy 1 is used as a hardening agent.
．． 3.5- 2% aqueous solution of triazine sodium salt 13
1.5 mQ of ma and glyoxal aqueous solution (40%)
added.

Similarly to Example 2, after coating the backing layer on one side of the film base coated with the antistatic layer, the emulsion layer, protective layer, and conductive layer were coated on the other side with the configuration shown in Table 3. was applied and dried in the same manner as in Example-1, and sample No. (57)-
No. (70) and comparative samples (g) and (h) were obtained.
The obtained samples were evaluated for antistatic performance and scratch resistance in the same manner as in Examples 1 and -2. Table 3 shows the results.
Shown below.

The attached drawings show an example of the layer structure of the antistatic silver halide photographic material according to the present invention, and the numbers in the drawings represent the following.

1: Antistatic layer 2: Conductive layer 3: Protective layer 4: Photosensitive silver halide emulsion layer 5: Backing lower layer 6: Packing upper layer 7: Subbing layer As is clear from Tables 2 and 3 above, this When the conductive layer according to the invention is used in a photosensitive material consisting of a tabular silver halide emulsion layer, or when used on the side of a backing layer containing an antihalation dye, excellent antistatic performance and scratch resistance can be achieved. Showing resistance.

Note that no abnormality was observed in the photographic characteristics of these samples.

〔Effect of the invention〕

According to the present invention, a silver halide photographic material is obtained which has high resistance to scratches and maintains antistatic performance even after processing. Such effects of the present invention were remarkable in X-ray silver halide photographic materials for rapid processing.

[Brief explanation of drawings]

FIGS. 1 to 10 are cross-sectional views showing examples of the layer structure of the antistatic silver halide photographic material of the present invention.

Claims (1)

[Claims] On at least one side of the support, there is an antistatic layer made of a reaction product of (1) a water-soluble conductive polymer (2), hydrophobic polymer particles (3) a curing agent, and at least one layer of A silver halide photographic light-sensitive material having a hydrophilic colloid layer has at least one conductive layer between the hydrophilic colloid layer closest to the support and the layer adjacent thereto and/or in the outermost layer. A silver halide photographic material characterized by: