JPH03282455A - Silver halide photographic sensitive material having improved antistatic performance - Google Patents

Abstract

PURPOSE:To obtain high sensitivity without adversely affecting photographic characteristics and to improve antistatic performance by incorporating a water soluble, electrically conductive polymer and a specified surfactant into an emulsion layer and/or a hydrophilic colloidal layer. CONSTITUTION:At least one kind of water soluble, electrically conductive poly mer and a surfactant represented by formula I, II etc., are incorporated into an emulsion layer and/or a hydrophilic colloidal layer. In the formula I, II R is alkyl, alkenyl, etc., each A1-A5 is a divalent combining group, m is 1-50, n is 0 or 1, B is H, <=6C alkyl or a hydrophilic group, R' is H or alkyl, Z is alkyl, aralkyl, etc., X is an anionic group and r is 0 or 1. A sensitive material having high sensitivity and superior antistatic performance is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material that is highly sensitive and has improved antistatic performance.

[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 exposed to light 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 line spots,
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, during manufacturing processes such as coating, drying, processing and packaging of photosensitive materials, as well as during film loading, photographing, processing in automatic processing machines, and projection, contact friction between various rollers, equipment, and photosensitive materials must be avoided. There are so many opportunities.

Methods of improving the conductivity of supports and various coated surface layers of photosensitive materials have been known for a long time. For example, NaCQ, LI
C (1, various hygroscopic substances and water-soluble inorganic salts such as KNOs, certain surfactants described in U.S. Pat. No. 2,982,651, U.S. Pat. No. 21922, 5g-20
The methods described in No. 8743, No. 59-74554, etc. have been attempted. However, with many of these conventionally known antistatic agents, depending on the type of support and the type of photographic composition, the confectionery may deteriorate, or if used in large amounts to achieve sufficient effect, the photographic properties may deteriorate. have a negative impact on
There were quite a few things to scrub.

Particularly in recent years, there has been an extremely strong demand for improved antistatic ability, and a solution to this current situation is desired.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material which has high sensitivity and excellent antistatic performance without adversely affecting photographic properties.

[Structure of the invention]

The above object of the present inventor is to provide a silver halide photographic material having at least one light-sensitive silver halide photographic emulsion layer and a non-light-sensitive hydrophilic colloid layer on at least one side of a support. and/or the hydrophilic colloid layer contains at least one water-soluble conductive polymer and a surfactant represented by the following formula [E], (I [), [■], [■] A silver halide photographic light-sensitive material and a photosensitive silver halide grain are characterized in that the grain has a portion containing 8 mol % or more of silver iodide, and the silver iodide content of the entire grain is 3. 5 mol% or less, silver bromide content 9
Silver halide monodisperse grains of 0% or more, or silver iodide content of 4.0 mol% or less, silver bromide content of 90% or more, and a grain diameter to thickness ratio of 4.0 to less than 30 This is achieved by a silver halide photographic light-sensitive material characterized by being a silver halide emulsion containing 50% or more of tabular grains.

-Formula CI) R-AI-(CB, CHCHJ)ffi-(AX)n-
Bol General formula (Ir) G-R' R-m, -N・-G-R' (Z)r(Xe)r General formula (III) Rf-A4-(CH*CHCHt)II-(Ax)n −
Bol (General formula (IV) GR' [wherein, R represents an alkyl group, an alkenyl group, or an aralkyl group, which may be further substituted.
;, they range from 8 to 25 carbon atoms A1, A2, A
3, A5 represents a divalent linking group, m is 1 to 50,
n represents 0 or 1. B represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a hydrophilic group.

G represents H consisting of units of -f CH2CHOH and -(CHx CHCH20h, (R1 represents a hydrogen atom or CH, - group, a represents 0 or 1 to 50, b represents 1 to 50, etc.) R' represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 6 or less carbon atoms.

2 represents an alkyl group, an aralkyl group, a carboxyl group-containing alkyl group, or a sulfonic acid group-containing alkyl group. They may also be further substituted. X represents an anion group, and r represents 0 or l.

R represents a saturated or unsaturated heptadoxycarbon group in which all or part of the hydrogen atoms are replaced with fluorine atoms, and the number of carbon atoms is 4.
~24 is preferred. ] Hereinafter, the present invention will be explained in detail.

First, the 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, it has a tendency to cause cracks in the layer due to fluctuations in drying conditions. In the structure of the present invention, hydrophobic polymer particles are contained in order to prevent cracking, and this effect is significant.

The water-soluble conductive polymer of the present invention includes a polymer 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 conductive group is required to be present in an amount of 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.

Specific compound examples 0xNa 03Na CH.

03Na SO, Na 5O,Na C0゜ So, Na 03Na 03Na CH, C00CH, CH20H So, Na 5O, Na M#900,000 =25 03Na x:y:z:v=60:30:8:2 M″=, 800,000 M”=t30,000 x:y:z:w-40:30:20:10M#500,000 MmjLl power CH.

force x:y:z=40:30:30 M1=F500,000M#300,000In addition, in the above P-1 to P-37, x, y, and z represent the mole% of each monomer component. , and M is the average molecular weight (
In this specification, average molecular weight refers to number average molecular weight).

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 log per unit m2 in terms of solid content, and is particularly preferably added. Add 0.05g to 5g.
Is Rukoto.

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

In the present invention, it is preferable to include hydrophobic polymer particles in the water-soluble conductive polymer layer, which is effective for preventing cracks.

The hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are substantially insoluble in water.
Contained in tex form. This hydrophobic polymer is
It is obtained by polymerizing monomers selected in any combination from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. In particular, at least 30 mol% of styrene derivatives, alkyl acrylates, alkyl methacrylates
It is preferable that it be contained. Particularly preferred is 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 and finely dispersing it, followed by distilling off the solvent.
It is possible to produce particles with a fine particle size and uniform grain size.
Emulsion polymerization is preferred. As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant, and it is preferably 10% by weight or less based on the monomer.

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.

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

Specific examples of hydrophobic polymer particles (L-5) CI(3 (L-1) (L-6) Cll.

(L-2) M = 500,000 M - 200,000 (L-8) (L-4) Q M - 600,000 M - 200,000 M - 150,000 The organic conductive polymer in the conductive layer used in the present invention is A sulfonic acid group or its base is bonded directly to an aromatic ring or heterocyclic group or via a divalent linking group, and has a molecular weight of 1 to 10 million, particularly preferably 1 to 10 million.
500,000 compounds. The polymer can be easily synthesized by polymerizing monomers that are commercially available or obtained by conventional methods.

The conductivity of the conductive polymer of the present invention refers to the surface specific resistance of 1010 Ω/c+5 (2
3°020%RH) or less.

The surface of the conductive 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 corona discharge geography;
It is preferable to process at a rate of l a+v −1 kw/m 2 ·min. Particularly preferable energy intensity is 08l
It is in the range of v −1w/m2·min.

A conductive layer coating liquid mixed with an organic conductive polymer, hydrophobic polymer particles, and a curing agent according to the present invention is coated on a support after subbing. For the purpose of strengthening the conductive layer film,
The degree of crosslinking can be set to any desired degree.

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

Next, the surfactants represented by general formulas CI) to [IV) of the present invention will be explained.

Preferred specific examples of R in formulas [■] to (IV) are (n) CaH+y (n)C+aLsC,H,3
CHCH2 and d represents 1 to 10) Specific examples of B include a hydrogen atom, CFI3- -COOM.

5o3AI, -0503M.

0 P-(OM) 2 (M represents a cationic group such as a hydrogen atom, an alkali metal, or ammonium.) C, □H
3s C0NHCH2CHt S- 0N- (R2 represents an alkyl group having 1 to 10 carbon atoms).

0(CHzCHO), =(R3 is a hydrogen atom or CH, -
(a represents 0 or 1 to 50).

A specific example of A2 is -gCH2day, -soCH, CHO,? -,.

2 dishes f-CH20HO), (CH, u-a CR3,
a has the same meaning as above (R) R5 represents an alkyl group or an aralkyl group, which may be substituted. Also, the alkyl portion preferably has 6 or less carbon atoms. For example, C
Represents H3- group, C-mount group, -cH,0 group, etc. R1 represents an alkylene group and preferably has 6 or less carbon atoms. For example, -CH2, C1(2C[(2(C[(2) represents 3 groups, etc.).

xe represents an anion group. For example, it represents CQ, Br, etc. ) In addition, - formula (I), CI [[] is general formula I), [)
It also includes a type in which (AZ)-B in (AZ)-B is bonded to a secondary OH group of a glyceryl group.

A specific example is SOx NH (CH2+7- (e represents 2 to 10)
CH, CH4 (d represents ~lO) -SO,NHCHICH C0NH (CH2)! NHCH2CH! = NHCHzCHzCH! -CH.

A specific example of 2 is 5OzNH (CH2 juice, C0NFI (CH2 juice, -C
H, C00e -(CH, T-coo.

,6CH,Soup SO,.

CH.

As a specific example of -C0N-CH2CL- C2H.

ChzCHzNf((CHz)s- (SO4)’/z Examples include.

Specific examples of A include glyceryl group-containing carbonized -CI (, CH2O(CH, CHO□) (R3 is a hydrogen atom or CH, - group hydrogen surfactants used in the present invention, but Without limitation, a represents 0 or ~50.

Specific examples of R (Ri has the same meaning as above, R7 represents an alkyl group such as CH3-1 CJs -1C3H7- group), CaHty()(-CH2Cl(zoh(:CHzC
) ICFIxO'hHH H cr*HssIfcHxcHx(:)"l'T"+Mr.C
H, CHCH, 0iE1H H H 0 mouth H H No. 0 1 (17 H L) H C-13 CI, H,, C00 (CIll, CH ρ soup type CH, C8
0 day HH C15l(s Ic0O(CHzCHCEIzOh('
CHzCH#rrHwl C,, a, Ic00(CH,CthOsuF'(C1(
zcHcHzNo cHzcHzO')TCaHr tB CtJ2s-3-(CH*CHi TKCH2CHCH
* ()hElH υh fi+b -15 c+d-5 H =27 h =28 H H υi H H H ClsHs r CCD+CH2CHCH20 formula CHz
GHz screw H2CH2SO1NaH H H υh a+b=8. c+d-6 C C! at(s so (CH2(JICh20)3C
H3C4SO3NaH =38 Next, specific examples of the glyceryl group-containing fluorine surfactant used in the present invention will be shown, but the invention is not limited thereto.

CaF r t So zNcHzcHzo(CH2C
)lzo) z (CHz(JICHzO) s (C
H2) 4 SOa NaC3H a
OH H Cm F + r So 2NCH2CH20(Cl
zcHzo) t s (C)+xC)lcHzo)
z-(CHz)45O3NaC2H.

H H i CaF l 7SO! NCH2CI(,0(C3H,0
) 2 (CH2C)IcH! O) B(C)+2)
, 303NaC3H.

H H H CHl H(CFz)scHzo(CHzCHC[(zo)2o
(CHz)4SOxNaC-57C3H.

In the present invention, each of the above-mentioned surfactants may be used alone, or a plurality of them may be used in combination. Other surfactants, such as the fluorine-containing surfactant described in Japanese Patent Application No. 150808/1984, may also be used in combination.

A polyhydric alcohol having a molecular weight of 150 or less may be used in the silver halide emulsion layer of the constituent layers of the silver halide photographic material of the present invention in order to suppress the occurrence of fog and improve pressure resistance. Examples of this polyhydric alcohol include those having at least two hydroxyl groups in the molecule and having a melting point of 40° C. or higher.

Although the polyhydric alcohol can be contained in any layer, it is preferably added to the silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto, and more preferably added to the photosensitive silver halide emulsion layer. It is to be. The content of polyhydric alcohol is not particularly limited, but one side of the support
The amount may be in the range of 0.1 to 2.0 g, more preferably 0.
．． 2-1. It is Og.

Although the timing of addition is arbitrary, it is preferably added between the end of chemical sensitization and the coating step. As for the addition method, it may be directly dispersed in a hydrophilic colloid, or it may be added after being dissolved in an organic solvent such as methanol or acetone.

The polyhydric alcohol used in the present invention has 2 to 6 hydroxyl groups in the molecule, 2 to 8 carbon atoms, and the hydroxyl group is not conjugated with a conjugated chain, that is, an oxidized base. An alcohol compound having a total molecular weight of 150 or less, preferably 100 or more, and 150 is preferable. Furthermore, the melting point is 40℃ or higher, 300℃
These are as follows.

Specific examples of polyhydric alcohols that can be preferably used in carrying out the present invention are listed 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-bentanediol 1-5 2.2-dimethyl-1,3-propanediol 1 -6 2,2-dimethyl-1,3-pentanediol 2, 2,4-trimethyl-1,3-bentanediol 2, 5-hexanediol 2, 5-dimethyl-2,5-hexanediol 1, 6-
Hexanediol i. to-decanediol 1,12-octadecanediol 1,18-octadecanediol cis-2,5-dimethyl-3-hexane-2,5-diol 1,13-tridecanediol pentamethylglycerin 2-butene-1.4 -diol 2,5-dimethyl-3-hexyne-2,5-diol 2
, 4-hexadiyn-1,6-diol 2,6-octadiyn-1,8-diol 2-methyl-2.3.4-butanetriol 2,3,4-hexanetriol 2,2-dihydroxymethyl-1- Butanol erythritol 1-25 2.5-dimethyl-2.3.4.5-hexanetetrol 1-26 1.2.5.6-hexanediol 1-2
7 1.3.4.5-hexanetetrol 1-28
1.6-(erythro-3.4)-hexanetetrol 1-29 2-dihydroxymethyl-1-butanol The light-sensitive silver halide grains of the silver halide photographic light-sensitive material of the present invention contain iodine inside the grains. It has a part containing silver iodide at 8 mol% or more, preferably 8 to 40 mol%, and the silver iodide content of the whole grain is 3.5 mol% or less, preferably 0.8 to 3.0%. , and the silver bromide content is 90% or more,
Preferred examples include photosensitive silver halide emulsions having monodispersed silver halide grains of 90 to 97%.

Furthermore, 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. is 9
0% or more, preferably 90 to 99%, and the ratio of particle diameter to thickness is 4.0 or more and less than 30, preferably 5.0% or more, preferably 90 to 99%.
50% or more of tabular grains of 0 to 20, preferably 40 to 20
Examples include photosensitive silver halide emulsions containing 90%.

By using these silver halide emulsions, it is possible to obtain a silver halide photographic material which has high sensitivity and satisfactorily achieves the desired effects of the present invention.

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

Layers that are then coated on top include, for example, hydrophilic colloid layers such as silver decagenide photographic emulsion layers, antihalation layers, interlayers, or backing layers. Preferably it is a photosensitive silver halide emulsion layer or a backing layer.

The upper layer may then be coated with, for example, a protective layer, an interlayer, a /X silver halide photographic emulsion layer, a filter layer, a development control layer, an antistatic layer, an ultraviolet absorbing layer, and the like. Preferably, a protective layer or a silver halide emulsion layer having substantially no photosensitivity is used.

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 emulsion used in the silver halide photographic material of the present invention can be structured by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978) - pages 22-23, 1.
ionPreparation 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" by T., Fl. James.
of thephotographic processes
s″ 4th edition, published by Macmillan (1977) 3
The method described on pages 8 to 104, "Photographic emulsion chemistry" by G-F, Dauffin, "Photographic emulsion chemistry"
ulsionChei+1stry% Focal
Press (1966), P, G1afkid
“Physics and Chemistry of Photography” by Chisie etphy
Paul
Published by Monte 1 (1967), V, L, Zeli
“Production and Coating of Photographic Emulsions” by Ksan et al. “Slaki
ng and coating photography
icemulsion” Published by Focal press (
(1964) and others.

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

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

Examples of silver halide emulsions preferably used in the present invention include JP-A-59-177535 and JP-A-61-802.
No. 237, No. 61-132943, No. 63-4975
1 and Japanese Patent Application No. 63-238225. Crystal walls are cubic, tetradecahedral, octahedral, and the intermediate (1, 1,
1) plane and (1,0,0) plane may be arbitrarily mixed.

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 silver halide grain. 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.

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

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

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.

As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using seed crystals and supplying silver ions and niolide ions using the seed crystals as growth nuclei is particularly preferred. Note that methods for obtaining core/shell emulsions include, for example, British Patent No. 1.027.146 and US Patent No. 3,505,068.
No. 4,444.877, JP-A-60-14331
This is detailed in publications such as No.

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 improved spectral sensitization efficiency, improved graininess and sharpness of images, etc., as described in British Patent No. 2,112,157 and US Patent No. 4,4.
39.520, 4,433.048, 4.41
No. 4,310, No. 4,434.226, Japanese Unexamined Patent Publication No. 1983-
No. 113927, No. 58-127921, No. 63-1
No. 38342, No. 63-284272, No. 63-30
It can be prepared by the method described in publications such as No. 5343.

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. good. 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 washed with water to remove soluble salts, such as the Tardel water washing method, the 7O curing sedimentation method, or the ultrafiltration method. As a preferable water washing method, for example, Japanese Patent Publication No. 35-16086
Particularly preferred desalting methods include a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in No. 1, or a method using a flocculating polymer agent such as G 3 and G 8 described in JP-A-63-158644. It will be done.

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). The following table lists the types of compounds and their descriptions in these two research disclosures.

Additives Chemical sensitizers Sensitizing dyes Development accelerators Antifoggants Stabilizers Color stain inhibitors Image stabilizers Ultraviolet absorbers Filters Dye sensitizers Hardeners Coating Auxiliary agents Surfactants Plasticizers Substrates Static inhibitor Matt agent Binder RD-17643 Page Classification 23 I [I 23 1'V 29 II+ 24 ■ 25 ■ 25 ■ 25~26 ■ 〃 〃 24 V 26 X 26~27 m 26~ 27 lI 27 n 〃 27 n 28! ■ 26 II RD-18716 Page Classification 648 - Upper right 648 Right - 649 Left 648 - Upper right 649 - Lower right 650 Left - Right 649 Right - 650 Left 651 Left 650 Right 650 Right〃 650 Right 651 Left Photosensitive material according to the present invention Supports that can be used include, for example, the aforementioned RD-17643, page 28 and RD
-18716, page 647, left column.

Suitable supports include plastic films, and the surfaces of these supports may be provided with a subbing layer or treated with corona discharge, ultraviolet irradiation, etc., in order to generally improve the 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 (1) Preparation of monodisperse grains Monodisperse grains of silver iodobromide containing 2.0 mol % of silver iodide with an average grain size of 0.22 μι were nucleated and containing 35 mol % of silver iodide. silver iodobromide at pH 3. It was grown at pA g7.5, and then potassium bromide and silver nitrate were added in equal moles at pH7.8 and pA g8.9, so that the silver iodobromide grains had an average silver iodide content of 2-1 mol%. Average particle size 1.46 μl (
A), 1.18μs (B), 0.73μm (C)
Monodispersed emulsion grains were prepared. The emulsion was desalted to remove excess salts using a conventional flocculation method. That is, while maintaining the temperature at 40°C, add a formalin condensate of sodium sodium sulfonate and an aqueous solution of magnesium sulfate, and after removing the supernatant liquid,
Pure water at 0°C was added to cause flocculation, and the supernatant liquid was removed. Next, add 5g of lime-treated gelatin and bring the total amount to 200c with water.
After finishing to c, the mixture was stirred at 50° C. for 30 minutes to disperse.

(2) Preparation of tabular grains Add 35 g of gelatin, 5 g of hydrium bromide, and 0.42 g of potassium iodide to water IQ, and add 5% to the solution kept at 65°C.
100 cc of silver nitrate aqueous solution and 100 cc of 0.73% potassium bromide aqueous solution were simultaneously added over 1 minute. Next, a silver nitrate aqueous solution containing 140 g of silver nitrate and a potassium bromide aqueous solution (containing 2.7 g of potassium iodide) were added simultaneously.

The addition rate at this time was gradually accelerated so that the rate at the end of the addition was seven times that at the beginning of the addition. After the addition, the pH was adjusted to 7.5.
The temperature was 50°C, and the sensitizing dyes SA and SB were added at 200:
The total amount was added at a weight ratio of 1/10 to 1,000 mg per mole of silver germide, and the mixture was stirred for 30 minutes. Thereafter, excess salt was removed as follows.

That is, A) After adding 50g of the compound described later to the reaction solution after particle formation at 40°C, 561t% of acetic acid was added to 10g of the compound described below.
After adding 5 cc and adjusting the pH to 5.0, it was allowed to stand and was decanted.

B) Then, after adding 1.912 g of pure water at 40°C, 6.5 g of caustic potassium was added, and the I) H was adjusted to 6.1, stirring was performed for 5 minutes, and then 65 cc of 56 vt% nO acetic acid was added, and the pH
After adjusting the temperature to 4.3, the mixture was allowed to stand still and decanted. B
) was repeated one more time. Furthermore, gelatin was added and dispersed with stirring in the same manner as in (1).

The resulting emulsion had tabular grains with a projected area diameter of 0.90 μm and an average grain thickness of 0.19 μm, and a tabular silver iodide content of 2.2 mol %.

(3) Preparation of twin emulsion grains No. 1 solution "H, 017ff K I 126 g L gelatin 210 g No. 2 solution "H, O 1
4Q K B r
3.5Kg duck acetic acid 0.356N
o, 3 liquids, -H, o 9.45QA
g N 03 4.2
Kg'NH,OH (concentrated ammonia water)3. H! No, 4
Liquid "N a I rCO61, OmQ'H, 0100m
a. While keeping the No-1 liquid at 46°C and stirring at 800 rpm, 3% of the volume of the N003 liquid was added at a constant rate over 1 minute, and after standing for 1 minute, the remaining NO12 liquid and N003 were added.
Start adding the NO12 solution at the same time, add the NO12 solution for 8 minutes, and then add the NO12 solution for 8 minutes.
Solution 83 was added at a constant rate over 14 minutes. After adding the N003 solution, 1 minute later, the No. 4 solution was rapidly added, and after aging for 2 minutes, acetic acid was added to adjust the pH to 6.0.

pAg was 11 while adding N082 and N013 solutions.
It changed to ~10.5.

Next, the monodisperse emulsion was desalted at the same time as the monodispersed emulsion, and gelatin was added to obtain 14.5 kg of an emulsion having a pH of 5.90 and a pA g of 8.71. The average particle size is r=0.51μ■,
The dispersibility of particle size is S/r = 0.24, and (
It was confirmed from the electron micrograph that the emulsion was a twin emulsion having 99% or more of ill) planes. The obtained emulsion was used as twin grains (3).

Sample preparation, processing and evaluation Each of the obtained emulsions was subjected to chemical ripening as follows.

For the emulsion thickened in (1), when each emulsion is mixed with the spectral sensitizing dyes SA and SB described later at a weight ratio of 200:1, the total amount of silver halide is After adding 750 mg per mole, ammonium thiocyanate @3.6X 10-” per mole
Chemical ripening was started by adding mol, and optimal amounts of chloroauric acid and hypo. 15 minutes before the end of the chemical ripening, 200 mg of potassium iodide was added per mole of silver, and then 1.8XlO-' of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added to complete the chemical ripening. .

In addition, for the emulsion obtained in (2), the sensitizing dye (same weight ratio) described below was added at 3°0
Add O−3 moles and optimal amounts of chloroauric acid and hypo;
Aged. After the ripening was completed, it was stabilized with 2.0XlO-'' of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene.

Emulsion additives described below were added to each emulsion to prepare an emulsion layer coating solution. However, for emulsion (1) (^):(
B):(C)-25:50:25 ratio.

In addition, the coating solution for the protective layer described below was prepared.

However, the surfactants shown in Table 1 were used.

The resulting emulsion layer coating solution and protective layer coating solution were coated to a thickness of 17 mm.
It was simultaneously coated on both sides of a 5 μm undercoated polyethylene terephthalate film base and dried for 2 minutes and 45 seconds to prepare a sample. The layer structure was an emulsion layer and a protective layer in order from the support.

Spectral sensitizing dye SA Spectral sensitizing dye SB (Film evaluation) Relative sensitivity measurement method The obtained sample was sandwiched between two fluorescent intensifying screens KO-250 (sold by Konica Corporation), and the tube voltage was 75 KVP. 12
The product irradiated with X-rays through an aluminum wedge under the conditions of 0 A was processed using an automatic processor manufactured by Konica Corporation (SKX-501) with XD-SR developer and XF-SR fixer at 45
Second processing was performed to determine the fog value and sensitivity of each sample.

Sensitivity depends on exposure, fog density +1.0 in base density
Find the reciprocal of the amount of light required to
It is expressed as a relative value when the sensitivity of 1 is set as 100.

Static mark generation test method The obtained film sample was stored in a dark room at a temperature of 23°C and a relative humidity of 2.
After conditioning the humidity for 2 hours under 0% conditions, the sample was rubbed with a neoprene rubber roller, and then the unexposed sample was developed using an automatic developing machine in the same manner as above, and the occurrence of scratch marks was visually confirmed.

Evaluation criteria 1: No occurrence 2: Very little occurrence (occurs in less than 1%) 3: Occurrence is somewhat common (occurs in less than 5%) 4: Occurrence is common (occurs in 5% or more) 5: Occurrence Extremely frequent (occurs in 50% or more) The value within 0 is the ratio to the total processing area. Further, numbers 1 to 3 pose no practical problems, but numbers 4 to 5 are not practical.

Method for measuring surface resistivity: The developed sample was sandwiched between brass back electrodes with an electrode spacing of 0.14 cm and a length of 10 cm, using an ultra-precise meter T R8651 manufactured by Takeda Ri.
The mold was measured for 1 minute. In addition, the sample was heated at 23°C and RH 20%.
The product was used after being conditioned for 4 hours under the following conditions.

As is clear from Table 1 above, the samples according to the present invention are highly sensitive and have excellent antistatic performance.

〔Effect of the invention〕

ADVANTAGE OF THE INVENTION According to the present invention, it was possible to provide a silver halide photographic material having high sensitivity and excellent antistatic performance.

Claims (1)

[Scope of Claims] 1) A silver halide photographic material having at least one light-sensitive silver halide photographic emulsion layer and a non-light-sensitive hydrophilic colloid layer on at least one side of a support, the emulsion layer and/or in the hydrophilic colloid layer, at least one
Seed water-soluble conductive polymer and the following general formula [I], [
A silver halide photographic material characterized by containing a surfactant represented by [II], [III] or [IV]. 2) As a photosensitive silver halide grain, the grain has a portion containing 8 mol% or more of silver iodide, the silver iodide content of the entire grain is 3.5 mol% or less, and the silver bromide content is Silver halide monodispersed grains of 90% or more, or silver iodide content of 4
．． A silver halide emulsion containing 50% or more of tabular grains with a silver bromide content of 0 mol% or less, a silver bromide content of 90% or more, and a grain diameter-to-thickness ratio of 4.0 or more and less than 30. The silver halide photographic material according to claim 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents an alkyl group, an alkenyl group, or an aralkyl group, which may be further substituted. In addition, they range from 8 to 25 carbon atoms, A_1, A_2
, A_3, A_4, A_5 represent a divalent linking group, m represents 1 to 50, and n represents 0 or 1. B represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a hydrophilic group. G represents the unit consisting of ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼. (R_1 is a hydrogen atom or CH_2- group,
a represents 0 or 1-50, and b represents 1-50. ) R' represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 6 or less carbon atoms. Z represents an alkyl group, an aralkyl group, a carboxyl group-containing alkyl group, or a sulfonic acid group-containing alkyl group. They may also be further substituted. X represents an anion group, and r represents 0 or 1. R_1 represents a saturated or unsaturated fluorinated carbon group in which all or part of the hydrogen atoms have been replaced with fluorine atoms, and the number of carbon atoms thereof is preferably 4 to 24. ]