JPH0473747A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the performanceof an antistatic layer by forming the antistatic layer consisting of a water-soluble conductive polymer, etc., on a base and icorporating liquid or fine granular solid paraffin having a specific grain size or below, etc., into material constituting layers. CONSTITUTION:The antistatic layer consisting of the water-soluble conductive polymer, the reaction product of a hardener and water-soluble polymer is formed on the bas and the layer contg. the liquid or fine granular solid paraffin having >=5mum grain size and/or a layer contg. wax on the surface is formed in the photographic sensitive material constituting layers. The excellent performance as the antistatic layer is obtd. in this way and the film peeling and sticking of the photographic coated layer are prevented.

Description

[Detailed Description of the Invention] [Industrial Field] The present invention relates to a method for preventing static electricity on silver halide photographic light-sensitive materials, and more specifically, it relates to a method for preventing static electricity on silver halide photographic materials. It relates to photographic materials.

C. Background of the Invention] -a. Plastic films have strong electrostatic properties, and there are many examples where this imposes many restrictions on use.

For example, supports such as polyethylene terephthalate used in silver halide photographic materials are particularly susceptible to charging at low humidity. Antistatic measures have recently become important when high-speed photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed to light through automatic printers.

When a photosensitive material is charged, static marks are generated due to the electrical discharge, or foreign substances such as dust are attached, which causes pinholes and significantly degrades the quality. I drop it. Therefore, antistatic agents are generally used in photosensitive materials, and recently, fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, sulfonic acids or phosphorus Polymers having acid groups in their molecules are used.

However, in photosensitive materials in which such an antistatic layer is coated on the surface of a support and then various photographic constituent layers, including the upper emulsion layer, are coated, the film tends to peel off during film handling. A so-called dry membrane defect was pointed out.

Particularly in recent years, as film transportation has become faster, the counter pressure on the film has become stronger, making it easier for the film to peel off, resulting in serious accidents. Another new problem is that when automatically transporting film one sheet at a time,
It was pointed out that there was a transportation problem where the two sheets stuck together and came out, and there was a strong desire for an immediate improvement along with the addition of a membrane.

[Purpose of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material which has excellent performance as an antistatic layer of a silver halide photographic light-sensitive material. A second object of the present invention is to provide a silver halide photographic light-sensitive material which is antistatic and has no peeling or sticking of photographic coating layers. Other objectives will become apparent from the description below.

[Structure of the invention]

As a result of various studies, the inventor of the present invention has found that the above objects can be achieved to a certain extent as follows, and has completed the present invention. That is, in a silver halide photographic material comprising a photosensitive silver halide emulsion layer coated on at least one side of a support, a water-soluble conductive polymer and a cured layer are coated on at least one side of the support. (1) has an antistatic layer made of a water-soluble polymer, and in the constituent layers of the photographic light-sensitive material,
This is achieved by a silver halide photographic light-sensitive material that is characterized by containing at least one of a layer containing liquid or fine-grained solid paraffin with a particle size of 5 μm or less and/or a layer containing Wanx on the surface.

The present invention will be explained in detail below.

The water-soluble conductive polymer according to the present invention is a molecule j11 in which a sulfonic acid group or its base is bonded directly to an aromatic ring or a heterocyclic group or via a divalent linking group.
000 to 1,000,000, particularly preferably 1 to 500,000. The polymer can be easily synthesized by polymerizing heptamers that are commercially available or obtained by conventional methods.

The conductivity of the conductive polymer of the present invention means that the specific resistance of the surface applied alone on a polyethylene terephthalate film of 2 g/m" or more is 10" Ω/cm (23 ° C
20%RFI) 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 a corona discharge treatment, which is preferably carried out at a rate of 1 kv/a"min.A particularly preferred energy intensity is 0.1 w.
This is the range of l w/+”・en.

Further, it is preferable to provide an adhesive layer made of gelatin or a gelatin derivative on the conductive layer of the present invention, and these adhesive layers can be overlaid at the same time as the conductive layer is applied, or can be applied after drying. This adhesive layer is 70℃~2
Preferably, the heat treatment is performed in a temperature range of 00°C. Various hardening agents can be applied to this adhesive layer, but from the viewpoints of crosslinking of the lower conductive layer and the upper backing layer, acrylamide-based, aldehyde-based, aziridine-based, begutide-based, evoquine, etc. Hardeners can be selected from hardeners such as hardeners, vinyl sulfone hardeners, and vinyl sulfone hardeners.

A conductive layer coating liquid containing a conductive polymer and latex is coated directly onto the support or after being coated on the support. For the purpose of strengthening the conductive layer film, the crosslinking degree can be set to any desired degree.

However, in order to achieve the desired performance, the mixing ratio of the conductive polymer and latex, the coating and drying conditions of the conductive layer,
Since the selection of the crosslinking agent and the amount used etc. have an influence, it is preferable to set good conditions. By setting these conditions, a preferable degree of crosslinking of the conductive layer after coating and drying can be determined. The degree of swelling was determined by immersing the sample of the present invention in pure water at 25° C. for 60 minutes, and attaching an adapter that could measure the thickness of the swollen film in water.

The degree of swelling can be determined by observing with an electron microscope and comparing it with the film thickness when dry. The degree of swelling can be determined by the thickness of the film swollen by immersion/thickness of the film when dry. To indirectly determine the degree of swelling, 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.
The volume increased by this water can be determined, and the film thickness can be determined from the specific gravity to determine the degree of swelling. Such a method can be applied not only to the swelling degree of the conductive layer but also to the banking protective layer, banking layer, silver halide emulsion layer, etc.

The thickness of the conductive layer is closely related to conductivity, and since the characteristics improve with an increase in unit volume, it is better to make it thicker, but the flexibility of the film will be impaired, so it should be 0.1 to 1.
Good results can be obtained by setting the thickness within 0.00 μm, particularly preferably within the range of 0.1 to IO μm.

Specific examples of the water-soluble conductive polymer according to the present invention will be shown below, but the present invention is not limited thereto.

503) Ja 03Na 03Na So, Na 5o, Na CH 2 COOCH x CH z OHM 900,000 SO, Na So , Na = 20 M'':, 800,000 x:y = 60:40 M' = 30,000 M≠30 10,000 x:y:z:v=40:30:20:10M#500,000x:y:z=40:30:30 M#500,000In addition, in the above P-1-P-37, X+ Y+ 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)
represents.

It should be noted that the polymers most useful in the practice of the present invention have an average molecular weight of about 10 million to about 1 million, as described above.

The amount of the conductive polymer contained in the conductive layer of the silver halide photographic light-sensitive material of the present invention is preferably 0.001g-1og per m2 in terms of solid content, particularly preferably 0.05g. ~5g.

When a conductive polymer is used in the undercoat layer/backing layer, banking protective layer or silver halide emulsion layer, the solid content equivalent amount is 0. It is preferable to use 10 g.

Next, (1) the reaction product of the curing agent according to the present invention will be described.

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

(1) Blocked isocyanate type (2) Multifunctional aziridine type (3) a-cyanoacrylate type (4) Epoxy type containing triphenylphosphine (5)
It is a trifunctional ethylene oxide type and is cured by electron beam or X-ray irradiation.

(6) N-methylol type (7) Metal complex containing zinc and zirconium metals (8) Silane coupling agent (9) Carboxy active type These hardening agents will be explained below.

(1) The blocked isocyanate curing agent used in the present invention is not particularly limited as long as it releases incyanate upon heating, but specific examples include (1) C21 (.

CH.

H OCH, CHU, H.

C.HS C2H.

■ 2H5 ■ C2H6 C,H.

■ The above compound may be dissolved in water or an organic solvent such as alcohol or acetone and added as is, or it may be dispersed using a surfactant such as dodecylbenzenesulfonate or nonylphenoxyalkylene oxide. It may be added from The preferred amount added is 1 to 1000 mg/m2.

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

Here, R1 is a hydrogen atom, an alkyl group having up to 20 carbon atoms, or
: represents an aryl group, a hydroxyl group, or a halogen atom, and R2 represents a hydrogen atom or an alkyl group having up to 10 carbon atoms.

The following are preferably used, but the invention is not limited thereto.

Next, the a-cyanoacrylate compound (3) used in the present invention is represented by the following general formula.

[In the formula, R is a substitution having 1 to 12 carbon atoms, Represents a kill group. ] unsubstituted al Specific examples are shown below. limited to this isn't it.

3-2 Next, the curing agent (4) containing an epoxy group used in the present invention is not particularly limited, and the compounds shown below are preferably used as specific examples.

Specific Example Compounds ■\/O The above compounds are mostly commercially available and can be easily obtained. The addition method may be by dissolving it in water or an organic solvent such as alcohol or acetone and adding it as is, or by dispersing it using a surfactant such as dodecylbenzene sulfinate or nonyl phenoxyalkylene oxide. It may be added from The preferred addition amount is 1 to 1000
mg/m2.

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

[In the formula, R and -R represent a substituted or unsubstituted alkyl group, hydrogen atom, halogen atom, nitro group, cyan group, hydroxy group, or alkoxy group. ] Triphenylphosphine is not particularly limited, but as specific examples, the compounds shown below are preferably used.

Next, the trifunctional ethylene oxide compound (5) used in the present invention is represented by the following general formula.

CH2=CII L Ct (=CH2 [In the formula, L represents a substituted or unsubstituted alkylene oxide silver group.] Specific examples are shown below, but the invention is not limited thereto.

Specific example CH2-CHCO(OCH2CH2)+0OCC1(=
CthCH2seCHCO(OCH2CH2)soOcc
H=cH2CH, C)1. c-(CH,0OCCE(=
CH2).

CfbCH2C(CH20CH2CHzOOCCt(=
CTo)sCH, (H3 CI+ 2= CCQ(OCH□GHz)z300cc
=cHzCH3 CH2=CHC00(CH2CI'bO)a(CHzC
HO)2(CHzCHzO)<0CCH= CH2CH
.

CH3CH2(CH200CC=CH21)3In addition, conventional bifunctional ethylene oxide compounds were crosslinked by a heating method to cure them, but this method causes slow reaction and insufficient crosslinking, resulting in low efficiency. It is characterized by being cured by electron beam or X-ray irradiation.

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

Electron beam intensity: 10-”-10’KW/m” (50
KW/m" is particularly preferred.) X-ray intensity: 10-2-106 KW/m" (30
0 KW/m" is particularly preferable.) Next, the N-methylol compound used in the present invention (6
), but the present invention is not limited thereto.

6-16-2 CH20H Next, specific examples of the metal complex (7) containing zinc and zirconium metal used in the present invention will be shown, but the invention is not limited thereto.

7-17-2 Zn(NH3)*CCH3CO0)2 Z
n(NH,), CO3(NHt)JnOH(COi)x The amount of the metal complex used is preferably 10-1 to 103 mol per mol of the conductive polymer.

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

In the present invention, the following silane fogging agent (8) can also be used as a curing agent.

82NC82C112NHCH,C)12cH2si(
(OCL)3CI□=CH5ICOC11s)s A carpoquine group-activated curing agent (9) is also used in the present invention. For example, the following carbodiimide type curing agents are used.

CH2CHCHzOCHzCHiCH2St(OCHx
)s\,/ Next, ① water-soluble polymer according to the present invention will be explained.

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

For example, for 100g of water at 20°C, 0.05
It is sufficient that it dissolves about 1 g or more, preferably 1 g or more. It is preferable that the water-soluble polymer used has a high solubility in the developing solution or fixing solution, and it is preferable that the solubility is 0.05 g or more, and more preferably 0.5 g or more in 100 g of the developing solution. Particularly preferred are those which dissolve 1 g or more.

Water-soluble polymers may be natural or synthetic.

Among the water-soluble polymers that can be used in the present invention, synthetic water-soluble polymers include those having, for example, nonionic groups, anionic groups, and both nonionic and anionic groups in their molecular structures. can be mentioned. Examples of nonionic groups include ether groups, ethylene oxide groups, and hydroquine groups.

Examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and the like.

The synthetic water-soluble polymer may be a homopolymer or a copolymer. The copolymer may be a copolymer with a partially hydrophobic monomer, as long as the polymer itself is water-soluble.

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

Natural water-soluble polymers include those with nonionic groups, anionic groups, etc. in their molecular structures,
Examples include those having both a nonionic group and an anionic group.

Preferred water-soluble polymers include those containing repeating units of the following general formula CW), particularly those containing 10 to 100 mol % of this in one polymer molecule.

General formula [W] (including those with substituents; for example, phenylene groups and those with substituents attached thereto), aralkylene groups (including those with substituents; for example, R1 and R7
may be the same or different, and each represents a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those with substituents; for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) , and those with substituents attached thereto), a halogen atom, or -CH, C00M.

L is -CONH-1-NHCO-1-COO-1-OC
O-1-CO-1SO, -1-NH5O, -1-3O,
Represents NH- or -〇-.

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

For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc., and those with substituents, etc.), aryle 1,000 GHz C) ICH
20+-+CH2+, (m is an integer of 0 to 40, n is an integer of HO to 4).

0M CR,°represents a hydrogen atom or R1, where M represents a hydrogen atom or a cationic group, and R9 represents an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group,
R3, R4, R6, R7 and R8 are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, propyl group). , phthyl group, hexyl group, denyl group,
(hexadecyl group, etc. or those with these substituents)
, alkenyl groups (e.g., vinyl groups, aryl groups, etc., or those with substituents attached to them), phenyl groups (e.g., phenyl groups, methoxyphenyl groups, chlorophenyl groups, etc., or those with substituents attached to them), aralkyl groups ( For example, it represents a benzyl group or the like (f: a substituent), X represents an anion, and p and q each represent 0 or 1.

In particular, polymers containing acrylamide or methacrylamide are preferred.

Y represents a hydrogen atom or ÷L+-+J-)TQ.

The synthetic water-soluble monomer constituting the unit represented by the general formula CW) can be copolymerized with ethylenically unsaturated heptano-. Examples of copolymerizable ethylenically unsaturated monomers include styrene, alkylstyrene, hydroquine alkylstyrene (the alkyl group preferably has 1 to 4 carbon atoms, such as methyl, ethyl, butyl, etc.), and vinylbenzenesulfonic acid. and its salts, α-methylstyrene, 4-
Vinylpyridine, N-vinylpyrrolidone, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, vinyl propionate, etc.), ethylenically unsaturated monocarboxylic or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, etc.) ), maleic anhydride, esters of ethylenically unsaturated carboxylic or dicarboxylic acids (e.g. n-butyl, l-late, N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate) , ethylenically unsaturated molar carboxylic acids or amides of carboxylic acids (eg, acrylamide, sodium 2-acrylamido-2-methylpropanesulfonate, N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine), and the like.

Next, specific examples of synthetic water-soluble polymers having repeating units of general formula (W) will be illustrated, but of course the compounds are not limited to these. Number written in Naorikko ÷ CHzCH + TI7
-+CHzCt(-Soup "CONH. CO
ONa (9,000) co. cooH CH.

-(-CH, -C+Tr8- W-17 C) 13 (However, nl: n2-50 mol% 50 mol%, thousands Average molecular weight - approx. 10,000) (However, H,: n, = 75 mol%: 25 mol%, several thousand average molecular weight approximately 20,000) (-CH2 CH→n−→CH.

C00CH, CI (20H CH”yrrr　C83 CONt(-CC)I2So,Na CH.

(8,000) CH2CH20H (9,000) (11,500) When using the above synthetic water-soluble polymer, the molecular weight is preferably 1,000 to 100,000, more preferably 2,000 to 50,000. use.

Natural water-soluble polymers that can be used in the present invention include those described in detail in the Comprehensive Technical Data Collection of Water-Soluble Polymer Water-Dispersible Resins (published by Management Development Center Publishing Department). In particular, lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin, guar gum,
Gum arabic, pectin, casein, agar, xanthanzam, nclodextrin, locust bean gum, gum tragacanth, carrageenan, glycogen, laminaran, lignin, nigeran, etc., and derivatives thereof are preferred.

Derivatives of natural water-soluble polymers include sulfonated, carboxylated, phosphorylated, sulfoalkylenated, or carboxyalkylenated, alkyl phosphorylated ones;
and its salts, polyoxyalkylenes (e.g. ethylene,
Preferred are glycerin, propylene, etc.) and alkylation (methyl, ethyl, benzylation, etc.).

Two or more types of natural water-soluble polymers may also be used in combination.

Among natural water-soluble polymers, glucose polymers and derivatives thereof are preferred, and among glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, nigeran, etc. are preferred, and dextran and derivatives thereof are particularly preferred. preferable.

Dextran is a polymer of σ-1.6 bonded D-glucose, and is generally obtained by culturing dextran-producing bacteria in the presence of sugars, but it is obtained from a culture of dextran-producing bacteria such as Leuconostoc and Mesenteroides. It can be obtained by reacting isolated dextran sucrase with saccharides. In addition, these native text runs are reduced to a desired molecular weight by a partial decomposition polymerization method using acid or alkaline enzymes, and the intrinsic viscosity is reduced to 0.
03 to 2.5 can also be obtained.

Examples of modified dextran include dextran@acid ester, carboxyalkyldextran, and hydrooxynealkyldextran.

It will be done. The molecular weight of these natural water-soluble polymers is 1000
~10,000 is preferred, particularly preferably 2,000 to 5
Ten thousand.

Methods for producing these dextrans and their derivatives are described in Japanese Patent Publication No. 35-11989 and U.S. Pat. No. 3.762.
．． No. 924, Special Publication No. 45-12820, No. 45-18
No. 418, No. 45-40149, No. 46-31192
listed in the number.

In the present invention, the synthetic or natural water-soluble polymer is preferably contained in the photosensitive material in an amount of 10% or more, more preferably 10% or more and 30% or less of the total weight thereof.

In addition to the above-mentioned water-soluble polymers, the present invention will discuss, for example, the hydrophobic polymer described in Japanese Patent Application No. 1-44106.Next, the paraffin according to the present invention will be described.

The paraffin used in the present invention is not particularly limited, and any commercially available paraffin may be used.

In general, paraffin is a mixture of higher paraffinic hydrocarbons represented by the formula CnH2n+, where n represents a natural number.Depending on the raw material and its refining method, paraffin is classified into solid paraffin and liquid paraffin. Any of them can be applied.

Liquid paraffin is preferred in terms of ease of handling.

As the liquid paraffin or fine particulate solid paraffin with a particle size of 5 μm or less used in the present invention, for example, liquid paraffin or solid paraffin manufactured by Chuo Kasei Co., Ltd. can be used.
The solid particle size of these paraffins is preferably 5 μm or less, preferably 1 μm or less. If the particle size is too large, the transparency of the coating film will deteriorate and the stability of the coating liquid and dispersion liquid over time will not be excellent.

To prepare a dispersion of solid paraffin having the above particle size according to the present invention, the solid paraffin is dissolved in a low boiling point solvent to form a solution, and then placed in water containing a protective colloid such as gelatin and a surfactant using, for example, a homogenizer. Disperse and manufacture. It is preferable to remove the low boiling point solvent by heating, reducing pressure, or the like.

In the present invention, the amount of paraffin added to the photographic constituent layer is usually 5% to 10% by weight based on the hydrophilic binder.
The content is preferably 0% by weight, but 10% to 50% by weight is particularly preferred.

The photographic constituent layer to be added may be an emulsion layer, a protective layer, an intermediate layer, or another layer adjacent to the emulsion, and in the case of an emulsion layer, it is desirable to add it after chemical ripening.

Next, the wax according to the present invention will be explained.

The wax used in the present invention may be natural or synthetic, and is a thermoplastic substance that is opaque in the solid state and is substantially insoluble in photographic processing solutions and the like.

Specifically, preferred examples include fatty acid esters, triesters, and tetraesters of polyhydric alcohols having 12 or more carbon atoms.

Specific compound examples are listed below, but the present invention is not limited thereto.

No.

C) 12-OCC,,H23 CH20CC++Hz3 CH□−〇cc　,　+　l(□.

CF2 0CC161137 ■ CH20CC+5Hxy CI□-〇CC1aHsy CH20CC17H36 H20H CH20CCl bHs r CH20CC+ sHi + I Also, as another type, derivatives of carboxylic acids having 12 or more carbon atoms and their salts, the following are also used as preferred waxes. .

(10) Cl6FI! Ic0OH (11) Cz+[l*3COOH (12) C23LaCOOH (13) Cl 7835CONH2 (14) C+yLsCOOC+aHxt (15) C2
+HttCOOC+yLs(16)C211(43CO
OC151(31(17)C1yHs5COOK (18)(CzHzaCOO)Jg (19)(C16H31COO)2A12 Furthermore, esters having a fluorinated alkyl as shown below can also be preferably used.

(20) H(CF,)3COOC4Hl(21) C
F3(CF2)lOcOOc6)+13(22) C,
Hl(CF,)12COOC,l(,3 In addition, molecular weight 2
000 or less polyethylene compounds are also used as waxes.

The above compounds are all known compounds and are easily available as commercial products.

When these waxes are used, for example, acetone, ethyl acetate, phenol, resorcinol, benzene, xylene, toluene, etc. can be used as a solvent.

In a preferred embodiment of the present invention, the conductive layer according to the present invention is coated on a subbing-treated support, and then a layer constituting a silver halide photographic light-sensitive material, such as a silver halide emulsion layer, and an intermediate layer are formed on the conductive layer. layers, dye layers, protective layers, etc. are applied. The paraffin or wax according to the present invention may be added to any of the constituent layers of the light-sensitive material, but it is more preferably used in the protective layer, which is the uppermost layer of the constituent layers of the light-sensitive material. The emulsion used in the silver halide photographic light-sensitive material of the invention may be any silver halide such as silver iodobromide, silver iodochloride, and silver iodochlorobromide, but it is said that one with particularly high sensitivity can be obtained. From this point of view, silver iodobromide is preferable.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
The crystal may be entirely isotropically grown like a tetrahedron, a polygonal 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 0.1
The particles may be fine particles of .mu.m or less to large particles of 20 .mu.m.

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. 47643 (1978
February) - Pages 22-23 1. Emulsion manufacturing method (Emulsi
onPreparation and types)
and same (RD) No. +18716 (November 1979
It can be prepared by the method described on page 648.

The emulsion of the silver halide photographic light-sensitive material according to the present invention, for example, "The theory" by T. H. James
of thephotographic processes
s” 4th edition, published by Maca + i fan (197
7) Method described on pages 38-104, G, F, Dauf
``Photograph Emulsion Chemistry J'' by fin
ic emulsion Chemistry, F
Published by ocal press (1966), P, GIa
“Physics and Chemistry of Photography” by fkides
tphysique photograhique”
Published by Paul Monte1 (1967), v, t
, ``Production and Coating of Photographic Emulsions'' by zet1kman et al.
'Making and coating photo
graphics+wulsion” Focal p
It is prepared by the method described in, for example, Published by Res Inc. (1964).

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.

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

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 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 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 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. 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 halide ions using the seed crystals as growth nuclei is particularly preferred. In addition,
Methods for obtaining core/shell emulsions are described in detail in publications such as British Patent No. 1,027.146, U.S. Patent No. 3,505,068, U.S. Pat. It is being

The silver halide emulsion used in the present invention may be tabular grains having 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,
It can be prepared by methods described in publications such as No. 310 and No. 4,434,226.

The emulsion mentioned above 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 a Tardel water washing method, a flocculation sedimentation method, or an ultrafiltration method. A preferred method of washing with water is, 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 not described in Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 18716 (November 1979). The types of compounds and locations listed in these two research disclosures are listed on the vestibule.

AdditivesChemical sensitizersSensitizersDye development acceleratorsAntifoggantsStabilizersColor stain inhibitorsImage stabilizersUltraviolet absorbersFiltersDye sensitizersWhitenersHardening agentsAuxiliary agentsSurfactantsPlasticizersSliding agents Static inhibitor mat agent binder RD-17643 Page Classification 23 In 23 IV 29 XXI 24 Vl // // 25 ■ 25 ■ 25~26 ■ // // 24 V 26 X 26~27XI 26~ 27 m 27 XI [ 27 Supports that can be used for such photosensitive materials 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 generally be provided with a subbing layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to 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 referred to here refers to high-energy xFii
waves, meaning 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 0.2 μm were used as nuclei, and silver iodobromide containing 30 mol% of silver iodide was prepared at pH= 9.3. It was grown at pAg=7.5, and then equimolar amounts of potassium bromide and silver nitrate were added at pH-7.8 and pAg=8.9, so that the average silver iodide content was 2.
．． Average grain size 1.15 to give 3 moles of silver iodobromide grains
μm (A), 0.63μs (B), O-42gm
Monodisperse emulsion grains of (C) were prepared. The emulsion was desalted to remove excess salts using a conventional flocculation method. That is, keep it at 40°C,
A formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added to cause agglomeration. After removing the supernatant liquid, pure water up to 40°C was further added, and an aqueous solution of magnesium sulfate was added again to cause flocculation, and the supernatant liquid was removed.

Sensitizing dye■ 2Hs C21(.

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

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

Further, regarding the particles (A), chemical sensitization was performed by the following method. 350 mg each of spectral sensitizing dyes ■ and ■, lQm
H/Agx] mol was added and mixed, ammonium thiocyanate, chloroauric acid and hypo were added to perform gold-sulfuric acid sensitization. Then, 4-hydroxy-6-methyl-1,3,
3a, stabilized by adding 7-chitrazaindene.

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

The following additives were added to the emulsion layer per mol of AgX.

t-Butylcatechol 400mg Polyvinylpyrrolidone (molecular weight 10000) 1.0g Trimethylolpropane 10g Diethylene glycol 5g Nitrophenyl-triphenylphosphonium chloride 50mg 1.3-
Ammonium dihydroxybenzene-4-sulfonate
4mg Sodium 2-mercaptobenzimidazole-5-sulfonate
15n+g1, l',; methylol-1-
Fromu 1-nitromethane 10+ng Styrene-maleic anhydride copolymer 2.5 gl-phenyl-5-methcaptotetrazole mg The following compounds were added to the protective layer for gelatin Ig.

Colloidal silica (average particle size 0.013μ111) CJ
,, -0÷CHzCt(20) + ocHzcHzo
t1mg C, F, mg for 7S03 Polymethyl methacrylate (matting agent) with an average particle size of 5μm 1g 0mg 2% aqueous solution of 2.4-dichloro-6-hydroquine-1,3,5-triazinna].lium salt 10ml
2CIl□-CHS O□CFI 20CH! So□
CH=CH, an appropriate amount, and as shown in Table 1, liquid paraffin and wax according to the present invention were added.

Regarding liquid paraffin, liquid paraffin 70
Dissolve 0g in 300mff of ethyl acetate, add 20g of gelatin
0g, Nirasan Oil Alkanol-X C10%26
After mixing and adding 3.6Q of 00+12° pure water to the solution kept at 60°C after swelling, 250 kg was added using a pressurized homogenizer laboratory type manufactured by Manton-Gaulin in the United States.
/ cal to obtain a liquid paraffin dispersion with an average particle size of 0.13 μm.

Using the same method, the temperature was kept at 80°C and the average particle size was 0.22.
Solid paraffin dispersions of μm were prepared and these two dispersions were used. Further, the wax used was obtained by dissolving the sample in acetone, adding diethyl phthalate and di-n-butyl phthalate, and dispersing with an ultrasonic homogenizer in the presence of a dispersant.

Next, the following supports were used.

After biaxial stretching, both sides of a 180 μm thick polyethylene terephthalate support were subjected to corona discharge treatment.

After applying the latex resin cited in Synthesis Example (1) described in Example 1 of JP-A No. 59-18945, p. 299, on top of the resin, the corona discharge treatment is performed again.

After the corona discharge treatment, the conductive layer according to the present invention was applied to the upper layer using a roll-fit coating pan and an air knife at a speed of 30 m/1 nin to the coating amount shown in Table 1 below, and then the above-mentioned conductive layer was applied again. Similarly, activation treatment by corona discharge was performed to obtain a support for use in the present invention.

The above-mentioned silver halide emulsion and protective layer coating solution were uniformly coated on both sides of the obtained support. Samples Nos. 1 to 30 were prepared by applying the gelatin amount to 6.0 g/m'' and the silver amount to 4.0 g/m2 on both sides.

The 30 types of samples thus produced were measured and evaluated using the following method.

(Measurement of surface resistivity) A test piece of the sample was placed with an electrode spacing of 0.14 m and a length of 10 c+a.
It was placed between brass electrodes and measured for 1 minute using a Riken insulation meter model TR8651. The sample was heated at 25°Cl2O%R,H,
The humidity was adjusted for 2 hours and then measured.

(Evaluation of two-sheet conveyance using auto feeder) Using auto feeder KDA-500 (manufactured by Konica),
The number of times two sheets are transported when 500 sheets are transported in 5 sets of 100 sheets is shown.

(Dry film test) Make shallow scratches on the emulsion surface of the sample with a razor in the shape of the base.
The remaining rate of the emulsion film relative to the adhesive area of the cellophane tape when the cellophane adhesive tape was pressure-bonded thereon and then rapidly peeled off was expressed as a percentage.

Comparative Polymers (A) (B) (C) As is clear from Table 1, the samples according to the present invention have good film adhesion and are antistatic without deteriorating transportability.

Example 2 In the same manner as in Example 1, an emulsion coating solution and a protective layer coating solution were prepared.

Next, in the same manner as in Example 1, the emulsion coating solution and the protective layer coating solution were simultaneously coated in multiple layers on one side of a support coated with the conductive layer according to the present invention on both sides, to prepare 24 types of samples.

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

<Backing layer> (Backing lower layer liquid) Lime-treated gelatin 70g acid-treated gelatin 5g trimethylolpropane per coating solution IQ
1.5g backing dye (see below) 1
．． og backing dye (see below) 1.0g (
Backing upper layer liquid) Coating liquid IQ: 70g lime-treated gelatin 5g trimethylolpropane
1.5g Backing Dye A Backing Dye B N03 C+ OH2+C0NH (CHzCH20) J2H5 1.0g 1.0g 0.5g 1.5g Punking Dye A F,,C,0(CH2CH2O)1. cH, CH, OH
0.1 g Liquid paraffin and wax - amounts listed in Table 2 The backing layer was simultaneously coated in multiple layers on the support coated with the conductive layer on the side opposite to the emulsion layer.

The sample obtained as described above was evaluated in the same manner as in Example-1.

2% aqueous solution of 2.4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 15a+72 Polymethyl having an area average particle size of 3.5 μm [Effect on the invention] The present invention prevents film peeling and sticking. It was possible to obtain an antistatic silver halide photographic material with no deterioration in physical properties.

Claims (1)

[Claims] In a silver halide photographic material comprising a photosensitive silver halide emulsion layer coated on at least one side of a support, (1) a water-soluble conductive polymer (2) is coated on at least one side of the support. ) a reaction product of a curing agent; and (3) a layer having an antistatic layer made of a water-soluble polymer, and containing liquid or fine-grained solid paraffin with a particle size of 5 μm or less in the constituent layers of the photographic light-sensitive material; A silver halide photographic material comprising at least one layer containing wax on its surface.