JP2796862B2 - Silver halide photographic material with improved antistatic properties and pressure resistance - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic material having improved antistatic properties and pressure resistance.

[Background of the Invention]

Since silver halide photographic materials generally consist of an electrically insulating support and a photographic constituent layer, they are subject to contact friction or peeling between the surfaces of the same or different substances during the manufacturing process and during use of the photographic material. Thereby, the electrostatic charge is easily accumulated. The photosensitive emulsion layer is exposed by the discharge of the electrostatic charge accumulated before the development processing, and when the photographic film is developed, spot-like spots or dendritic or feather-like spots,
This produces a so-called static mark. This significantly impairs the commercial value of the photographic film. For example, static marks appearing randomly in medical or industrial X-ray films can lead to very dangerous decisions, but this phenomenon is only apparent after development and is one of the most troublesome problems. In addition, these accumulated electrostatic charges may cause a second problem such as dust adhering to the film surface or uniform application.
It also causes a secondary failure. This static mark is more likely to occur due to high sensitivity of the photosensitive material, high speed coating, high speed photographing, high speed automatic processing, and the like.

In other words, in the manufacturing process including coating, drying, processing and packaging of photosensitive materials, and in contact with various rollers, equipment and photosensitive materials in the film device, photographing, automatic developing machine processing process or shadowing There are many opportunities for friction.

Conventionally, there has been known a method for improving the conductivity of a support of a light-sensitive material and various coating surface layers. For example, attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, and the like. I have been. However, many of these conventionally known antistatic agents, the type of support,
Depending on the type of the photographic composition, there are not a few that deteriorate the effect or have a negative effect on the photographic characteristics, and furthermore, there is not obtained one that satisfies the problem that the antistatic property is completely lost after the development processing. That was the current situation.

In particular, when applied to high-sensitivity silver halide photographic materials, undesirable fog called dry fog occurs during drying during film production, and furthermore, fog or reduction due to mechanical or physical pressure during film handling. Such effects tend to cause a negative effect on photographic characteristics such as feeling, and improvement thereof has been strongly desired.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material having significantly improved antistatic performance without adversely affecting photographic characteristics.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is free from fog due to rapid drying in the production of the light-sensitive material or bending during the handling of the light-sensitive material. It is.

A third object of the present invention is to provide a silver halide photographic material having no deterioration in antistatic performance even after development processing. Other objects will be apparent from the following description.

[Configuration of the invention]

The present inventor has conducted extensive studies on antistatic agents in view of such circumstances, and as a result, has found that these objects can be easily achieved by the following constitution, and has accomplished the present invention.

That is, an antistatic layer comprising a reaction product of (1) a water-soluble conductive polymer (2) a hydrophobic polymer particle (3) a curing agent is provided on at least one side of the support, The silver halide photographic light-sensitive material having on the body, characterized in that the light-sensitive silver halide emulsion layer of the light-sensitive material contains at least one selected from polyhydric alcohol compounds having a molecular weight of 150 or less. A silver halide photographic material and a photosensitive silver halide grain having a portion containing silver iodide of 8 mol% or more, the silver iodide content of the whole grain being 3.5 mol% or less, A silver halide monodispersed grain having a silver iodide content of 90 mol% or more, or a silver iodide content of 4.0 mol% or less and a silver iodide content of 9 mol% or less
The silver halide photographic light-sensitive material as described in the above item, which is a silver halide emulsion containing 50% or more of tabular grains having a ratio of grain diameter to thickness of 4.0 to less than 30 at 0 mol% or more. Easily achieved.

 Hereinafter, the present invention will be described in detail.

The present applicant has already proposed to improve the antistatic property by combining various curing agents with conductive polymers and hydrophobic polymer particles for the purpose similar to the present invention.
No. 330860 and No. 1-444106.

However, these techniques, while satisfying the antistatic performance, have not yet completely eliminated the problem of photographic performance given to high-sensitivity photosensitive materials.

The present inventor has conducted extensive studies on the antistatic layer and the conductive layer. As a result, the conductive layer described above was provided on the support coated with the undercoat layer, and a polyhydric alcohol having a molecular weight of 150 or less was used. By including the compound in the silver halide emulsion layer, an unexpected effect of suppressing fog and improving pressure resistance was obtained.

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

The water-soluble conductive polymer of the present invention can form a transparent layer even when used alone, but has the property of causing cracking of the layer due to blurring in drying conditions. In the constitution of the present invention, hydrophobic polymer particles are contained in order to prevent the cracks, and the effect is large.

Examples of the water-soluble conductive polymer of the present invention include polymers having at least one conductive group selected from sulfonic acid groups, sulfate groups, quaternary ammonium salts, tertiary ammonium salts, carboxyl groups, and polyethylene oxide groups. Among these groups, a sulfonic acid group, a sulfate group, and a quaternary ammonium base are preferable. The conductive groups require at least 5% by weight per polymer molecule.

Hereinafter, examples of the compound of the water-soluble conductive polymer used in the present invention will be described, but the present invention is not limited thereto.

Specific compound examples In the above P-1 to P-37, x, y, and z represent mol% of each monomer component or an average molecular weight (in the present specification, the average molecular weight indicates a number average molecular weight). .

Antistatic layers in silver halide photographic light-sensitive material of the present invention, and the amount of the conductive polymer contained in the conductive layer is the it is preferable to add 0.001g~10g per unit m ² in terms of solid content weight, particularly preferred Means to add 0.05 g to 5 g.

When the conductive polymer is used for the backing layer, the backing protection or the silver halide emulsion layer, the solid content is reduced to 0.
It is preferably between 01 and 10 g.

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

The hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are contained in a so-called latex state which is substantially insoluble in water. The hydrophobic polymer is a monomer selected from styrene, a styrene derivative, an alkyl acrylate, an alkyl methacrylate, an olefin derivative, a halogenated ethylene derivative, an acrylamide derivative, a methacrylamide derivative, a vinyl ester derivative, and acrylonitrile in any combination. Obtained by polymerization. In particular, it is preferable that at least 30 mol% of a styrene derivative, an alkyl acrylate, or an alkyl methacrylate is contained. In particular, 50 mol% or more is preferable.

There are two methods for converting a hydrophobic polymer into a latex by emulsion polymerization or by dissolving a solid polymer in a low boiling point solution and then finely dispersing the solvent, followed by distilling off the solvent. Emulsion polymerization is preferred in that a uniform product can be obtained. As the surfactant used in the emulsion polymerization, it is preferable to use an anionic or nonionic surfactant, and it is preferable that the surfactant be 10% by weight or less based on the monomer. A large amount of surfactant causes the conductive layer to become cloudy.

The molecular weight of the hydrophobic polymer may be 3000 or more, and there is almost no difference in transparency due to the molecular weight.

 Next, specific examples of the hydrophobic polymer of the present invention will be described.

The organic conductive polymer in the conductive layer used in the present invention is in a form in which a sulfonic acid group or a base thereof is directly bonded on an aromatic ring or a heterocyclic group or via a divalent linking group, and has a molecular weight of One to ten million, particularly preferably one to 500,000 compounds. The polymer can be easily synthesized by polymerizing a commercially available or conventional monomer.

The conductivity of the conductive polymer of the present invention means that the specific resistance of the surface is 10 ¹⁰ Ω / cm (23 ° C. 20% RH) when applied alone on polyethylene terephthalate film at 2 g / m ² or more.
It has the following characteristics.

The surface of the conductive layer of the present invention is preferably activated by corona discharge, glow discharge, ultraviolet light, flame treatment, or the like. A particularly preferred activation treatment is a corona discharge treatment, which is preferably performed at a rate of ¹ mw to 1 kw / m ² · min. Particularly preferred energy intensity is in the range of ^{0.1w-1w / m 2 · min} .

The conductive layer coating solution in which the organic conductive polymer according to the present invention is mixed with the hydrophobic polymer particles and the curing agent is applied on the support after the undercoating process. An arbitrary degree of crosslinking can be set for the purpose of strengthening the conductive layer film.

However, in order to obtain the desired performance, it is necessary to set good conditions because the mixing ratio of the conductive polymer and the hydrophobic polymer particles, the conditions for applying and drying the conductive layer, and the selection and use amount of the curing agent are affected. preferable.

In addition, a metal oxide can be used for the constituent layer of the present invention in order to further exert the effects of the present invention. As the metal oxide used in the conductive layer, any of indium oxide, tin oxide, a metal oxide doped with an antimony atom or a phosphorus atom, or a combination thereof can be used.

As indium oxide, indium oxide, (In
_{Although 2} O) and indium oxide (In ₂ O ₃ ) are known, in the present invention, it is preferable to use indium oxide.

Stannous oxide (SnO) and stannic oxide (SnO ₂ ) are known as tin oxide, but stannic oxide is preferably used in the present invention. Specific examples of the metal oxide doped with an antimony atom or a phosphorus atom include tin oxide and indium oxide.

In order to dope the metal oxide with antimony or phosphorus, a tin, indium halide, alkoxylate or nitrate compound and antimony or phosphorus halide, alkoxylate or nitrate can be mixed and oxidized and fired. . These metal compounds can be easily obtained. The content of antimony or phosphorus is preferably 0.5 to 10% by weight based on tin or indium. These inorganic compounds can be added by dispersing in a hydrophilic colloid such as gelatin,
Alternatively, it is preferable to disperse and add in a high molecular compound such as acrylic acid or maleic acid. The loading ratio per binder is preferably from 1 to 100% by weight.

Next, it is used for crosslinking the conductive layer of the present invention (3)
Examples of the reaction product of the hardener include hardeners for gelatin which are conventionally known as hardeners.

Hereinafter, specific compound examples of the curing agent particularly preferably used in the invention are shown below, but the invention is not limited thereto.

The polyhydric alcohol having a molecular weight of 150 or less used in the silver halide emulsion layer of the silver halide photographic light-sensitive material constituting layer of the present invention means a polyhydric alcohol having at least two hydroxyl groups in the molecule and having a melting point of 40 ° C or more. Is mentioned.

Although the polyhydric alcohol can be contained in any layer, it is preferably added to the silver halide emulsion layer or to the hydrophilic colloid layer adjacent thereto, more preferably to the photosensitive silver halide emulsion layer. It is to be. The content of the polyhydric alcohol is not particularly limited, but 1 m per side of the support.
It may be in the range of 0.1 to 2.0 g, more preferably 0.2 to 1.0 g
It is.

The timing of addition is arbitrary, but preferably it is added after the completion of chemical sensitization until the coating step. As an addition method, it may be directly dispersed in a hydrophilic colloid, or methanol,
It may be added after being dissolved in an organic solvent such as acetone.

The polyhydric alcohol used in the present invention has 2 to 6 hydroxyl groups in the molecule, has 2 to 8 carbon atoms, and the hydroxyl group is not conjugated with a conjugated chain, that is, an oxidized type. Alcohol diameter compounds having a total molecular weight of 150 or less, preferably 100 or more, and 150 are preferable. Further, it has a melting point of 40 ° C. or more and 300 ° C. or less.

Specific examples of polyhydric alcohols that can be preferably used in the practice of the present invention are described below, but those that can be used in the present invention are not limited to these specific examples.

1-1 diethylene glycol 1-2 glycerin 1-3 triethylene glycol 1-4 2,3,3,4-tetramethyl-2,4-pentanediol 1-5 2,2-dimethyl-1,3-propanediol 1 -6 2,2-dimethyl-1,3-pentanediol 1-7 2,2,4-trimethyl-1,3-pentanediol 1-8 2,5-hexanediol 1-9 2,5-dimethyl-2 , 5-hexanediol 1-10 1,6-hexanediol 1-11 1.10-decanediol 1-12 1,12-octadecanediol 1-13 1,18-octadecanediol 1-14 cis-2,5-dimethyl- 3-hexane-2,5-diol 1-15 1,13-tridecanediol 1-16 pentamethylglycerin 1-17 2-butene-1,4-diol 1-18 2,5-dimethyl-3-hexyne- 2,5-diol 1-19 2,4-hexadiyne-1,6-diol 1-20 2,6 Octadiyne-1,8-diol 1-21 2-methyl-2,3,4-butanetriol 1-22 2,3,4-hexanetriol 1-23 2,2-dihydroxymethyl-1-butanol 1-24 erythritol 1-25 2,5-dimethyl-2,3,4,5-hexane tetrol 1-26 1,2,5,6-hexane tetrol 1-27 1,3,4,5-hexane tetrol 1- 28 1,6- (erythro-3,4) -hexanetetrol 1-29 2,2-dihydroxymethyl-1-butanol Hydrophilicity in or adjacent to the antistatic layer of the silver halide photographic light-sensitive material of the present invention. A plasticizer can be used in the colloid layer for the purpose of providing plasticity.

Any plasticizer can be used as long as it exhibits a plasticizing action, but a polyalkylene oxide compound is preferably used.

The polyalkylene oxide compound used in the present invention is at least 2 or more, at most 500
Refers to a compound containing a polyalkylene oxide chain below, for example, a polyalkylene oxide and a fatty alcohol, a phenol, a fatty acid, an aliphatic mercaptan, by a condensation reaction with a compound having an active hydrogen atom such as an organic amine, or polypropylene glycol, It can be synthesized by condensing an aliphatic mercaptan, an organic amine, ethylene oxide, propylene oxide, or the like with a polyol such as a polyoxytetramethylene polymer.

The polyalkylene oxide compound may be a block copolymer in which the polyalkylene oxide chain in the molecule is divided into two or more instead of one. On this occasion,
The total polymerization degree of the polyalkylene oxide is 3 or more and 100
The following is preferred.

Specific examples of the polyalkylene oxide compound optionally used in the invention are shown below.

When the above compound is used in the present invention, the compound is dissolved in a hydrophilic solvent such as methanol, ethanol, methyl cellosolve or the like, and then (1) a water-soluble conductive polymer (2) hydrophobic polymer particles (3) according to the present invention. ) It may be added to an antistatic solution composed of a reaction product of a curing agent, or may be added to, for example, a gelatin layer, a silver halide emulsion layer, etc. which is coated adjacent to the antistatic layer.

Although the amount of addition is not uniform depending on the type of the compound, it is preferable to add 0.01 to 0.5 g, more preferably 0.03 to 0.3 g, per unit m ² in terms of solid content.

The photosensitive silver halide grains of the silver halide photographic light-sensitive material of the present invention contain at least 8 mol% of silver iodide therein.
It preferably has a portion containing 8 to 40 mol%, and the silver iodide content of the whole grain is 3.5 mol% or less, preferably 0.8 mol% or less.
~ 3.0% and the silver bromide content is 90% or more, preferably 9% or more.
And silver halide monodispersed silver halide emulsions of 0 to 97%.

Further, the photosensitive silver halide emulsion of the silver halide photographic light-sensitive material of the present invention has a silver iodide content of 4.0 mol% or less, preferably 0.1 to 3.5 mol%, and a silver bromide content of 90% or more, preferably Is a light-sensitive silver halide emulsion containing 90 to 99% of tabular grains having a grain diameter to thickness ratio of 4.0 to less than 30, preferably 5.0 to 20 at 50% or more, preferably 40 to 90%. Is mentioned.

By using these silver halide emulsions, it becomes possible to obtain a silver halide photographic light-sensitive material having high sensitivity and excellently achieving the object effects of the present invention.

Next, as a preferred embodiment of the present invention, an antistatic layer composed of a gelatin layer is provided as a hydrophilic colloid layer on a polyethylene terephthalate support coated with an undercoat layer.

The antistatic layer may have a structure of a conductive layer comprising (1), (2) and (3) according to the present invention, and may be a generally known surfactant (for example, JP-A-53-1983). No. 21922,
No. 58-208743, No. 59-74554, No. 60-80839, No. 60
Like those described) or an inorganic compound No. -94126 (e.g. NaCl, LiCl, KNO ₃₎ antistatic agents and metal oxides such as (e.g. JP 60-23848, the 58-62649 JP, the 57-
118242).

Preferably, a conductive layer having the former configuration is used. Next, as a layer to be coated thereon, there may be mentioned, for example, a silver halide photographic emulsion layer, an antihalation agent, a hydrophilic colloid layer such as an intermediate layer or a backing layer. Preferably, it is a photosensitive silver halide emulsion layer or a backing layer.

Then, a protective layer, an intermediate layer, a silver halide photographic emulsion layer, a filter layer, a development controlling layer, an antistatic layer, an ultraviolet absorbing layer, and the like may be coated on the upper layer. Preferably, a protective layer or a substantially insensitive silver halide emulsion layer is used.

The hydrophilic colloid layer referred to in the present invention refers to the hydrophilic property of a silver halide photographic material, and includes a binder component such as gelatin, for example, a silver halide emulsion layer, a protective layer, an intermediate layer, and a halation layer. Refers to various layers required for a photographic material such as an prevention layer, a filter layer, a development control layer, an ultraviolet absorbing layer, an undercoat layer, and a backing layer.

As described above, the conductive layer according to the present invention includes the types and mixing ratios of the conductive polymer (1) and the hydrophobic polymer particles (2), selection of the curing agent (3) serving as a cross-linking agent, amount used, and drying conditions. Is preferably set to an optimum condition.

The degree of crosslinking of the conductive layer by the curing agent can be known from the degree of expansion. For the degree of swelling, the sample of the present invention was immersed in pure water at 25 ° C. for 60 minutes, and an adapter capable of measuring the swelled film thickness in water was attached.

The degree of swelling can be determined by observing with an electron microscope and comparing with the film thickness when dried. The degree of swelling can be determined by the equation: swelling degree = film thickness swollen by immersion / film thickness after drying. To determine the degree of swelling indirectly, the amount of water absorbed is determined from the weight of a sample of a fixed area when dried and the weight of the sample when swollen, and the volume increased by this water is determined, and the specific gravity is determined. The swelling degree can be determined by determining the film thickness from the above equation. The preferred degree of expansion is 0.2 to 100%, more preferably 2 to 50%.

The thickness of the conductive layer is closely related to conductivity, and it is better to increase the thickness because the characteristics are improved by increasing the unit volume, but the flexibility of the film is impaired.
Within the range, particularly preferably within the range of 0.1 to 10 μm, good results can be obtained.

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, but particularly high sensitivity is obtained. From the viewpoint, silver iodobromide is preferred.

The silver halide grains in the photographic emulsion are cubic, octahedral,
They may be all isotropically grown, such as tetradecahedrons, polyhedral crystals such as spheres, twins having plane defects, or mixtures or composites thereof. The size of these silver halide grains is 0.1 μm
Large particles ranging from the following fine particles to 20 μm may be used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22-2
Emulsion Preparaition and typ
es) 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 in, for example, "The theory of the photographic material" by TH James.
Process, 4th edition, published by Macmillan (1977), pp. 38-104, GFDauffin, "Photographic Emulsion Chemistry", "Photogr
aphic emulsion Chemistry ", published by Focal press (1966
), P. Glafkidse, "Physics and Chemistry of Photography", Chimie et p.
hysique photograhique "published by Paul Montel (1967),
VLZelikman et al., "Manufacture and coating of photographic emulsions", "Making a
nd coating photographic emulsion "prepared by the method described in Focal press (1964).

That is, solution conditions such as neutral method, acidic method, ammonia method, etc., mixing conditions such as forward mixing method, back mixing method, double jet method, controlled double jet method, and particle preparation conditions such as conversion method, core / shell method, etc. And a combination thereof.

A preferred embodiment of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

Examples of the silver halide emulsion preferably used in the present invention include, for example, JP-A-59-177535, JP-A-61-802237, and JP-A-61-802237.
And the internal high iodine type monodispersed particles disclosed in JP-A-132943, JP-A-63-49751 and Japanese Patent Application No. 63-238225. The crystal wall of the crystal may be cubic, tetradecahedral, octahedral, and a mixture of (1,1,1) and (1,0,0) planes between them.

The monodisperse emulsion referred to herein means that at least 95% of the particles by number or weight are within ± 40% of the average particle diameter, preferably ±
The silver halide grains are within 30%. The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The crystal structure of the silver halide may be different from the silver halide composition inside and outside.

The emulsion according to a preferred embodiment of the present invention is a core / shell type monodisperse emulsion having a clear two-layer structure comprising a low iodine shell layer in a high iodine core portion.

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

Methods for producing such monodispersed emulsions are known, for example, J. Pho
t.Sic.12.242 to 251 (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, UK Patent
Nos. 1,413,748 and U.S. Pat. Nos. 3,574,628 and 3,655,394.

As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus is particularly preferable. As a method for obtaining a core / shell emulsion, for example, British Patent No. 1.027.146, US Patent Nos. 3,505,068, and 4,444,877
And JP-A-60-14331.

The silver halide emulsion used in the present invention may be tabular grains having an aspect ratio of 4 or more and less than 30.

The advantages of such tabular grains include, for example, improvement in spectral sensitization efficiency, improvement in graininess and sharpness of images, and the like, for example, UK Patent 2,112,157, US Patent 4,439,520,
Nos. 4,433,048, 4.414,310, 4,434,226, JP-A-58-113927, 58-127921, 63-138342,
It can be prepared by the methods described in JP-A Nos. 63-284272 and 63-305343.

The emulsion described above may be either a surface latent image type for forming a latent image on the grain surface, an internal latent image type for forming a latent image inside the grain, or a type for forming a latent image on the surface and inside. Good. These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as Nudel washing, flocculation sedimentation or ultrafiltration in order to remove soluble salts.
As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or a coagulated polymer agent exemplified by G3, G8 described in JP-A-63-158644, etc. The method used is a particularly preferred desalting method.

In the emulsion according to the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. 17643 (December 1978) and No. 18716.
(November 1979). The following table shows the types and locations of the compounds shown in these two research disclosures.

Examples of the support that can be used in the light-sensitive material according to the present invention include, for example, pages 28 and RD-18716 of RD-17643 described above.
Those described in the left column on page 647 can be mentioned.

A suitable support is a plastic film, etc.
Generally, the surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc., in order to improve the adhesion of the coating layer. Then, the emulsion according to the present invention can be coated on one side 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 the present invention is applied to medical X-ray radiography, for example, a fluorescent intensifying screen mainly containing a phosphor that generates near-ultraviolet light or visible light by exposure to penetrating radiation is used. It is desirable that this is brought into close contact with both surfaces of a light-sensitive material obtained by coating the emulsion of the present invention on both surfaces and then exposed.

The penetrating radiation referred to here is a high-energy electromagnetic wave and means X-rays and gamma rays.

The fluorescent intensifying screen is, for example, an intensifying screen mainly containing calcium tungstate as a fluorescent component, or a fluorescent intensifying screen mainly containing a rare earth compound activated with terbium.

〔Example〕

Hereinafter, embodiments of the present invention will be described. However, needless to say, the present invention is not limited to the embodiments described below.

Example 1 (1) Preparation of Monodisperse Grains Silver iodobromide containing 30 mol% of silver iodide with monodisperse grains of silver iodobromide containing 2.0 mol% of silver iodide having an average particle size of 0.2 μm as nuclei Is grown at pH 9.8 and pAg 7.8, and then equimolar amounts of potassium bromide and silver nitrate are added at pH 8.2 and pAg 9.1 to form silver iodobromide grains having an average silver iodide content of 2.2 mol%. Average particle size 0.3
75 μm ((1) -1), 0.64 μm ((1) -2), 1.42 μ
m ((1) -3) were prepared. The emulsion was subjected to desalting of excess salts by a usual aggregation method. That is, 40 ° C
, And a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added, and the mixture was aggregated and the supernatant was removed. The dispersibility of the three particle sizes obtained was S / <
0.16 had good dispersibility.

It was confirmed by X-ray diffraction that each silver halide grain contained a portion having 20 mol% or more of silver iodide inside the grain.

(2) Preparation of tabular grains 1.5% gelatin solution containing 0.17 mol of potassium bromide 5.5
While stirring at 80 ° C. and pH 5.9, 2.1 mol of potassium bromide and 2.0 mol of silver nitrate were added by a double jet method over 2 minutes. pBr was maintained at 0.8. (0.53% of the total silver nitrate used was consumed.) The addition of the potassium bromide solution was stopped and the silver nitrate solution continued to be added for 4.6 minutes. (This consumed 8.6% of the total silver nitrate used.) Then, a potassium bromide solution and a silver nitrate solution were added simultaneously for 13 minutes. During this time, the pBr was maintained at 1.2, and the addition flow rate was accelerated so that the completion time was 2.5 times the start time. (43.6% of the total silver nitrate used was consumed.) The addition of the potassium bromide solution was stopped and the silver nitrate solution was added for 1 minute. (Consumes 4.7% of the total silver nitrate used.) A 2.0 mol solution of potassium bromide containing 0.55 mol of potassium iodide was added along with the silver nitrate solution over 13.3 minutes. During this time, the pBr was maintained at 1.7 and the flow rate was accelerated to 1.5 times the starting rate upon completion. (Consumes 35.9% of the total silver nitrate used.) Add 1.5 g / mol Ag of sodium thiocyanate to this emulsion.
Was added and held for 25 minutes. 0.60 mol of potassium iodide and silver nitrate were added in a solution by a double jet method at an equal flow rate for about 5 minutes until the pBr reached 3.0. (About 6.6% of the total silver nitrate used was consumed.) The amount of total silver nitrate consumed was about 11 mol. Thus, an emulsion containing tabular silver iodobromide grains having an average grain diameter of 1.62 μm and an aspect ratio of about 16: 1 was prepared. This grain has the total projected area of the silver iodobromide grain.
Tabular grains accounted for over 80%.

 The resulting emulsion was designated as tabular grains (2).

(3) Preparation of polydisperse particles Keep the No. 1 solution at 46 ° C and stir at 800 rpm
o Add 3% of the volume of solution 3 at a constant speed over 1 minute, leave it for 1 minute, then start adding remaining No. 2 solution and No. 3 solution at the same time. , No. 3 solution was added at a constant speed over 14 minutes. One minute after the addition of the No. 3 solution, the No. 4 solution was rapidly added, and after aging for 2 minutes, acetic acid was added to adjust the pH to 6.0. The pAg changed from 11 to 10.5 while adding the No. 2 solution and the No. 3 solution.

Next, desalting was performed simultaneously with the monodispersed emulsion, and gelatin was added to obtain 14.5 kg of an emulsion having a pH of 5.90 and a pAg of 8.71. The average particle size is 0.51 μm, and the dispersibility of the particle size is S / = 0.
It was 24, and it was confirmed from the electron micrograph that it was a twin emulsion having (111) planes at 99% or more. The resulting emulsion was designated as polydisperse particles (3).

Preparation, processing and evaluation of sample Each of the obtained silver halide grains (1), (2) and (3) was added with pure water so that the volume per mole of silver was 500 ml, and then brought to 55 ° C. The total amount of the spectral sensitizing dyes A and B described below in a weight ratio of 200: 1 was 820 mg for (1) -1; 600 mg for (1) -2, and (1)-per mole of silver halide.
360 mg was added to 600 mg of tabular grains (2) and 700 mg to polydisperse grains (3).

Per mol of silver of ammonium thiocyanate after 10 minutes (1) -1 is 4 × 10 ^-3 mol, (1) -2 2 × 10 ^-3 mol, (1) -3 is 1 × 10 ^- mol, (2) was added in an amount of 2 × 10 ⁻³ mol, and (3) was added in an amount of 3 × 10 ⁻³ mol. Further, appropriate amounts of chloroauric acid and hypo were added to initiate chemical ripening. At this time
The pH was 6.15 and the silver potential was 50 mV.

Fifteen minutes before the end of chemical ripening (70 minutes after the start of chemical ripening), 200 mg of potassium iodide was added per mole of silver,
% (Wt / vol) acetic acid to lower the pH to 5.6 and
The pH value is maintained for 0.5 minutes and then 0.5% of potassium hydroxide (w
t / vol) solution was added to return the pH to 6.15, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to complete chemical ripening.

15% of (1) -1 and 50 of (1) -2 of the obtained particles.
% And (1) were mixed at a ratio of 35%, and the emulsion additives described later were added to prepare a monodisperse emulsion preparation liquid (emulsion 1).
The tabular grains of (2) and the polydispersed grains of (3) were similarly added with an emulsion additive to prepare a tabular emulsion preparation (emulsion 2) and a polydispersion emulsion preparation (emulsion 3), respectively. And

In addition, in addition to the additives described below, the following compound (1)
(2) A dispersion (a) in which (3) is dispersed to form oil droplets having a particle size of 0.12 μm, and a dispersion in which compounds (2), (3) and (4) are dispersed to form oil droplets having a particle size of 0.09 μm. Compound (b) was added in the following amount per mole of silver halide.

That is, Dispersion (a) was prepared according to the method described in Example 1, (3) of JP-A-61-285445, and
No. 243654, page 35, line 15 et seq., Dispersed in an amount corresponding to the above addition amount.

Additives used in the emulsion solution (photosensitive silver halide coating solution) are as follows. The amount of addition is shown in an amount per mole of silver halide.

Polyhydric alcohol compound of the present invention Table 2 Amounts described in Table 2 1.Phenyl-5-mercaptotetrazole 50 mg The additives used in the protective layer solution are as follows. The amount of addition is indicated by the amount per coating solution.

Incidentally, the emulsion 1.48 g / m ² in terms of silver value, all hydrophilic colloid amount such that 1.98 g / m ^2, the protective layer is such that 0.99 g / m ₂ as a weight with gelatin, the two A copolymer consisting of three monomers, 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate, and 40 wt% of butyl methacrylate, was diluted with a slide hopper type coater at a speed of 60 m / min to a concentration of 10 wt%. The resulting aqueous dispersion of the copolymer was uniformly coated on one side onto a 175 μm polyethylene terephthalate film base provided as a subbing liquid.

The film base provided with the conductive layer according to the present invention was prepared as follows.

That is, after performing a corona discharge on a 175 μm polyethylene terephthalate base provided with the aqueous copolymer dispersion as a subbing liquid, an antistatic liquid having the following composition was added at 10 ml / m ^2.
It was applied using a roll-fit coating pan and an air knife at a speed of 33 m / min.

(1) Water-soluble conductive polymer (described in Table 1) 0.6 g / m ² (2) Hydrophobic polymer particles (described in Table 1) 0.4 g / m ² (3) Curing agent (described in Table 1) 0.15 g / m ² [Plasticizer] (See Table 1) After applying 0.10 g / m ² , it was dried at 90 ° C. for 2 minutes and then heat-treated at 140 ° C. for 90 seconds.

Relative sensitivity measurement method The obtained sample was narrowed between fluorescent intensifying screens KO-250 (available from Konica Corporation), irradiated with X-rays at a tube voltage of 90 KVP, 20 mA for 0.05 seconds, and sensitized by the distance method. A metric characteristic curve was created. The development processing was carried out using an automatic developing machine (KX-500) manufactured by Konica Corporation with an XD-90 developing solution for 90 seconds, and the fog value and sensitivity of each sample were determined.

The sensitivity was calculated by calculating the reciprocal of the amount of light required to increase the blackening density by 1.0 by exposure.
It was expressed as a relative value when 0 was set.

Pressure resistance test method Two pieces of each sample were kept at 25 ° C and 35% relative humidity for about 12 hours under constant temperature and humidity conditions.
At 5 cm, it was bent about 280 mm. One of the two sheets was developed 3 minutes after bending without exposure. The difference between the density and the fog density of blackening part caused by bending at this time as a [Delta] D _1, and a measure of pressure blackening. In other words, the smaller this value is, the better the pressure blackening resistance is.

The other one of the two sheets was exposed and developed using an optical wedge three minutes after bending. The wedge blackening density of this sample was measured, and the density difference between the desensitized portion caused by bending at the density of 1.0 ± 0.1 and the unfolded portion was defined as ΔD _2, and ΔD at each density D _{2 The} value was divided by ₂ and the average value ΔD ₂ / D ₂ was calculated, and this value was used as a measure of pressure desensitization. In other words, the smaller the value, the better the pressure desensitization resistance.

Test method for stitch mark generation The obtained film sample was placed in a dark room at a temperature of 23 ° C and a relative humidity of 20.
After humidifying the sample for 2 hours under a% condition, the sample was rubbed with a neoprene roller, and then developed with an automatic developing machine in the same manner as described above, and the occurrence of stitch marks was visually checked.

Measurement method of surface specific resistance value The developed sample was narrowed to a brass electrode having an electrode interval of 0.14 cm and a length of 10 cm, and the measurement was performed for 1 minute using an insulation meter TR8651 manufactured by Takeda Science. In addition, the sample used after conditioning for 3 hours at 23 ° C. and 20% RH was used.

 The results obtained are shown in Table 2 below.

As is clear from Table 2 above, the sample according to the present invention did not decrease in sensitivity or increase in fog and was excellent in pressure resistance. In particular, the effect of the present invention is remarkable when a monodisperse emulsion (1) or a tabular grain emulsion (2), which is a silver halide grain having an internal high iodine content, is used as compared with the use of the polydisperse emulsion (3). You can see that there is.

Further, generation of static marks was not observed at all in the sample of the present invention, and the chargeability after the treatment was also improved.

Sample No. 32 was prepared in the same manner as Sample No. 11 except that the following VS-1 was used in an optimum amount as a hardener added to the protective layer, but the photographic properties, pressure resistance and antistatic properties were good. Met.

VS-1 H ₂ C = CHSO ₂ CH ₂ OCH ₂ SO ₂ CH = CH ₂ Example 2 (4) Preparation of monodisperse particles Monodisperse containing 2 mol% of iodine and 0.2 mol% of chlorine having an average particle diameter of 0.18 μm A silver iodobromide layer was provided at an inner nucleus of silver chloroiodobromide and outside thereof at a ratio of 40 mol% of iodine and 60 mol% of bromine, and was grown to a grain size of 0.45 μm. A silver iodobromide layer was grown at a ratio of 99 mol% up to 0.69 μm to obtain slightly rounded tetrahedral silver halide grains.

Thereafter, desalting was carried out by a coagulation method in the same manner as in the preparation of the monodispersed emulsion of the example.

As for dispersibility, good monodispersity was obtained at s / <0.16. or,
X-ray diffraction confirmed that the grains had a portion of silver iodide of 20 mol% or more inside.

(5) Preparation of average particles 32 g of gelatin, 11.0 g of potassium bromide and 12 cc of a 0.5% thioether (HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH) aqueous solution
To water 1 to form an aqueous solution,
After maintaining the pAg 9.2 and the pH at 6.6 and simultaneously adding all the solutions I and II shown in Table 3 over 40 seconds with stirring, the whole amount of the solution III shown in Table 3 was added over 8 minutes. Thereafter, all of the solutions IV and V shown in Table 3 were simultaneously added by the double jet method over 80 minutes to prepare silver halide grains.

The silver halide grains thus obtained had an average diameter of 1.27 μm and an average diameter / thickness ratio of 5.1.

(6) Preparation of polydisperse particles Comparative polydisperse emulsions were prepared by a positive mixing method.

Solution A: Nitric acid 100g Ammonia water (28%) 78cc Add water 240cc B Solution: Ossein gelatin 8g Potassium bromide 80g Potassium iodide 2.2g Add water 550cc Solution C: Ammonium water 6cc Glacial acetic acid 10cc Water 34cc D Liquid: 226 cc of glacial acetic acid and 400 cc of water were added to prepare the above four solutions (solutions A to D).

Next, the solution B and the solution C were poured into a reaction vessel for preparing an emulsion, and stirred with a propeller-type stirrer at 300 rpm to keep the reaction temperature at 45 ° C. Subsequently, the solution A was divided into a ratio of 1: 2: 2, and 100 ml of the solution was added to a mixed solution of the solutions B and C over 2 minutes. After stirring for 8 minutes, the remaining two volumes of Solution A, 200 ml, were added over 2 minutes, and stirring was continued for 15 minutes. Then, the solution D was added to the mixture of the solution A, the solution B, and the solution C to adjust the pH of the solution in the reaction vessel to 6, and the reaction was stopped. Thus, a comparative polydisperse emulsion having an average particle size of 0.71 μm (comparative) was obtained.

Preparation, processing and evaluation of sample Each of the obtained silver halide grains (4), (5) and (6) was added with pure water so that the volume per mole of silver was 500 ml, and then the temperature was raised to 55 ° C. Spectral sensitizing dyes A and B
In a weight ratio of 200: 1, 50 mg (4) per mol of silver halide, 500 mg for tabular grains (5) and 500 mg for polydisperse grains (6).

After 10 minutes, ammonium thiocyanate was added to (4) 1.8 × 10 ^-3 mol, (5) 1.8 × 10 ^-3 mol, and (6) per mol of silver.
2.5 × 10 ^-3 mol was added, and an appropriate amount of chloroauric acid and hypo were further added to start chemical ripening. The pH at this time is 5.95,
The silver potential was set at 60 mv.

The same emulsion additives as in Example 1 were added to each grain to form an emulsion layer solution.

 The same protective layer solution was used.

Incidentally, the emulsion 1.51 g / m ² in terms of silver value, all hydrophilic colloid amount such that 2.02 g / m ^2, the protective layer is such that 1.02 g / m ² as a weight with gelatin, the two Using a slide hopper type coater at a speed of 60 m / min, a copolymer consisting of three types of monomers, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, and butyl methacrylate 40 wt%, was diluted to a concentration of 10 wt%. The aqueous dispersion of the copolymer was uniformly coated on one side of a 175 μm polyethylene terephthalate film base provided as a subbing liquid.

The film base provided with the conductive layer according to the present invention used one shown in Table 4 below.

 Evaluation of the sample was performed in the same manner as in Example 1.

 Table 4 shows the obtained results.

As is clear from Table 4 above, as the silver halide grains, a silver halide monodispersed grain emulsion (No-4) having a portion containing silver iodide inside, or the ratio of the grain diameter to the thickness. It can be seen that the use of the tabular grain emulsion (No. 5) having the above-mentioned results in the effects of the present invention are better exhibited than in the case of the comparative polydisperse grains (No. 6).

〔The invention's effect〕

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

Such effects of the present invention were effective in a silver halide photographic light-sensitive material comprising silver iodobromide with high sensitivity.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-249047 (JP, A) JP-A-55-84658 (JP, A) JP-A-55-95942 (JP, A) JP-A-60-1985 143331 (JP, A) JP-A-63-88547 (JP, A) JP-A-63-104047 (JP, A) JP-A-59-500021 (JP, A) (58) Fields investigated (Int. ⁶ , DB name) G03C 1/85 G03C 1/06

Claims (2)

(57) [Claims] 1. At least one side of a support, (1) a water-soluble conductive polymer (2) hydrophobic polymer particles (3)
In a silver halide photographic light-sensitive material having an antistatic layer comprising a reaction product of a curing agent on a support coated with an undercoat layer, the light-sensitive silver halide emulsion layer of the light-sensitive material contains A silver halide photographic material comprising at least one selected from polyhydric alcohol compounds having a molecular weight of 150 or less. 2. The photosensitive silver halide grains have a portion containing 8 mol% or more of silver iodide inside the grains, the silver iodide content of the whole grains is 3.5 mol% or less, and the silver bromide content is Is 90 mol% or more, or silver iodide content is 4.0 mol% or less, silver bromide content is 90 mol% or more, and the ratio of grain diameter to thickness is 4.0 or more and less than 30. 2. The silver halide photographic light-sensitive material according to claim 1, which is a silver halide emulsion containing 50% or more of tabular grains.