JPS62286038A - Silver halide photographic sensitive material having good anti-static property - Google Patents

Abstract

PURPOSE:To obtain the titled material having a sufficient anti-static property at a low humidity by mounting one layer contg. a high polymer complex having ionic conductivity on a substrate body. CONSTITUTION:At least one layer contg. the high polymer complex having the ionic conductivity is mounted on the substrate. As the high polymer complex has the ionic conductivity, the layer contg. the higher polymer complex has the anti-static property. Said high polymer complex is composed of a polymer and a metal salt. The polymer is exemplified by a polymer contg. a monomer of polyethylene oxide unit, etc., especially, the polymer contg. the polyethylene oxide unit or the polyethylene imine unit. The metal salt is exemplified by an alkali metal salt such as sodium iodide and mercury chloride, etc., and the most preferably, the alkali metal salt such as hydrohalogenic acid.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having good antistatic properties. be.

[Background of the invention] Silver halide photographic material (hereinafter referred to as photographic material).

) generally consists of an electrically insulating support and photographic constituent layers, so they are susceptible to static electricity due to contact friction or peeling between surfaces of the same or different materials during the manufacturing process of photographic light-sensitive materials and during use. Electric charge is often accumulated. This accumulated electrostatic charge does not cause many problems, but the most serious one is that the photosensitive emulsion layer is sensitized by the discharge of the accumulated electrostatic charge before processing, and the photographic film is processed. When this occurs, dot-like spots or dendritic or feather-like lines are produced. This is what is called a static mark, and it significantly reduces the commercial value of photographic film. For example, if static marks appear on medical or industrial X-ray films, this can lead to very dangerous decisions. This phenomenon becomes apparent only after development, 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 uneven coating.

As mentioned above, such electrostatic charges are generated during the production of photographic light-sensitive materials.
5 and 1 are often accumulated during use, but for example, during the manufacturing process, contact friction between the photographic film and rollers, or separation of the support surface and the emulsion surface during the winding and unwinding process of the photographic film. Occurs due to etc. In addition, in finished products, the separation of the base surface and emulsion surface when the photographic film is wound and changed, or
Electrostatic charges are generated due to contact separation between the ray film and a mechanical part in an automatic camera or a fluorescent intensifying screen. It can also occur due to contact with other packaging materials. Static marks on photosensitive materials induced by such accumulation of electrostatic charges become more noticeable as the sensitivity of the photosensitive materials increases and the processing speed increases. Especially recently, the sensitivity of photographic materials has increased, high-speed coating, high-speed photography,
As the number of opportunities for harsh handling such as high-speed automatic development processing increases, star marks are more likely to occur.

In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic material. However, as antistatic agents that can be used in photographic light-sensitive materials, antistatic agents commonly used in other fields cannot be used as they are, and are subject to various restrictions unique to photographic light-sensitive materials. As an antistatic agent that can be used in photographic light-sensitive materials, in addition to its excellent antistatic performance, it does not have a negative effect on the film properties and adhesion resistance of photographic light-sensitive materials, and it does not cause fatigue in processing solutions for photographic light-sensitive materials. There are many restrictions on applying antistatic agents to photographic materials, such as not accelerating the process, not contaminating the transport rollers, and not reducing the adhesive strength between the constituent layers of photographic materials. There is.

One way to eliminate these problems caused by static electricity is to increase the electrical conductivity of the surface of the photographic material so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged.

Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. It's here.

Among these, surfactants have been found to be effective in antistatic ability; for example, US Pat. No. 3.082.123,
3,201,251@, 3,519,561, 3,625゜695, West German Patent No. 1,552゜4
No. 08, No. 1,597゜472, JP-A-49-858
No. 26, No. 53-129623, No. 54-15922
No. 3, No. 48-19213, Special Publication No. 46-39312
Anionic, betaine and cationic surfactants described in Japanese Patent No. 49-11567, No. 51-46755, No. 55-14417, etc.
80023, West German Patent No. 1.1122.809, West German Patent No. 1,4.22,818, Australian Patent No. 5
4.44L/1959, and ionene type polymers described in JP-A-53-92125 are known.

However, in the conventional antistatic agents as described above, the conductivity of these antistatic agents changes depending on humidity, and sufficient performance cannot be obtained particularly at low humidity.

For this reason, as a method for improving antistatic properties in low humidity environments, US Pat. A technique for dispersing in hydrophilic colloids has been disclosed.However, even with this method, the required sufficient antistatic performance cannot be obtained.A further improvement on this method is U.S. Pat. No. 4,542゜095. describes a technique in which an aqueous dispersion such as latex is mixed with a nonionic surfactant having a polyethylene oxide chain and an alkali metal salt, and then coated on a support to produce an antistatic layer. With this method, the antistatic properties vary depending on the conditions for forming the latex layer, and it has not yet been put to practical use.

In other words, in a system in which a nonionic surfactant having a polyethylene oxide chain and an alkali metal salt are mixed with a latex containing additives such as a hydrophilic colloid such as gelatin and an emulsifier, satisfactory antistatic properties cannot be obtained. .

[Object of the Invention] Therefore, an object of the present invention is to provide a silver halide photographic material having sufficient antistatic performance even at low humidity.

[Structure of the Invention] As a result of intensive research, the present inventors have developed a system in which a nonionic surfactant having a polyethylene oxide chain and an alkali metal salt are mixed into a latex containing additives such as a hydrophilic colloid such as gelatin and an emulsifier. It has been found that the reason why satisfactory antistatic properties cannot be obtained is that a uniform coating film cannot be formed depending on the coating liquid prepared by mixing these hydrophilic colloids or latex. .

The present inventors realized that the above problems could be solved if the polymer and metal salt could be coated without using binders such as hydrophilic colloids and latex, and conducted further research. As a result, if a polymer having a polyethylene oxide chain and a metal salt form a polymer complex, the polymer and metal salt can be dissolved in, for example, a polar solvent and applied completely uniformly, resulting in a good coating. It has been found that a coating film can be formed.

Therefore, the object of the present invention has been achieved by a silver halide photographic material comprising at least one layer containing an ion-conducting polymer complex on a support.

[Specific Structure of the Invention] Since the polymer complex according to the present invention has ion conductivity, a layer containing the polymer complex is provided with antistatic properties.

The polymer complex according to the present invention is not particularly limited, but preferably includes a polymer as shown below (hereinafter referred to as the polymer of the present invention) and a metal salt as shown below (hereinafter referred to as the metal salt of the present invention). It is a complex formed by

That is, one feature of the present invention is that the polymer of the present invention and the metal salt of the present invention form a polymer complex. Therefore, according to the polymer of the present invention and the metal salt of the present invention, a photographic constituent layer of a silver halide photographic light-sensitive material can be coated without using a conventional method of using a binder, such as dispersing it in a hydrophilic colloid or latex. can do.

Examples of the polymer of the present invention include polymers having monomers such as polyethylene oxide units, polypropylene oxide units, polymethyl vinyl ether units, polystyrene sulfide units, poly-β-caprolactone units, polyethylene succinate units, and polyethyleneimine units. In particular, polymers having polyethylene oxide units or polyethyleneimine units are preferred.

Examples of polymers having polyethylene oxide units include, but are not limited to, the following.

The following margin mountains
Mountain P-5 CnF2TT-1+CH2C)T20+mCnF2T1
-1n = 5~15 m-20~50? H3 H, +OCH2CH29 → O81 坩子CPh CL
O Kuran a-10~100 b=5~100 I”7 CHa CH3CHa CHa 〇(C2H409→C3Hs O%H a-5~100 C-5~50 1]=2~5Q d=o~50CH20+CH
2CH2O+H1.

a + c = 25-100 CH3 □ n = 1-20 R: Hl Alkyl paleo COO + CH2CH2O + R having 1-5 polymer n =
1-20 1R: H1 Polymer C2H4n = 3 having 20 molti or more of alkyl groups having 1 to 5 carbon atoms+CH2CH+ +A+ units and x y C-0 Recommendation These polymers are known, and the manufacturing method is described in U.S. Pat. No. 4.542.095, JP-A-61-41143
No. 61-47713, No. 60-199047, No. 60-1794.48, etc. In addition, some products are Pluronic P123 (BASF
(manufactured by BASF), Tetronics Tl304 (manufactured by BASF), Surfynol 465 (manufactured by Air Products 'A),
It is commercially available under the names of Q4-3667 (Gura Corning), Monoflow 51 (ICI), PSO71, PSO73 (Petrarch Systems), Silwet L-7605 (Union Carbide), and the like.

Furthermore, among the above-mentioned polymers having polyethylene oxide units, vinyl polymers such as P-9 to P-11 and P-13 can be combined with other copolymerizable vinyl monomers (A>
It may also be a copolymerization with.

Examples of other vinyl monomers (A) include, but are not limited to, alkyl acrylates, alkyl methacrylates, monoalkyl itaconates, dialkyl itaconates, acrylonitrile, acrylamide, vinyl acetate, styrene, divinylbenzene, glycidyl acrylate, Examples include monoalkyl maleate, dialkyl maleate, monoalkyl fumarate, dialkyl fumarate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. Two or more types of vinyl monomers (A) may be copolymerized.

Specific examples of the vinyl monomer (A), as well as the molar ratio and polymerization degree of the ethylene oxide monomer and the vinyl monomer (A>) are shown below, but the invention is not limited thereto.

Below margin A Molification x:y H cooc ratio C00CHzCH20H ■ +CH2CH+-60:40 1.0C00C
2H5 P-1,0 H3 ■ ■ +CH2-C-)-80:20 5■ 0OCR3 ■ +CH2cn-)-90:10 1.0■ COOC2H5 ■ +CH2CH+ 50:50
1.5N ■ +CH2-CH÷ 60: 40
1.0" C0CH5 x:y n C)I3 ■ +CH2C-)-5Q:50 100OC
H3 Coon C00CHa ■ ■ +CH2C÷ 30 Near 0 10COOCH3 ■ +CH2CH÷ 60:40
50■ C00C2H5 In addition, examples of polymers having polyethyleneimine units include, but are not limited to, the following.

E-1-+CH201-12NH-)-E-2-+CH
2C82N-)- □ -O R: Alkyl group having 1 to 5 carbon atoms The above polymer is known and the manufacturing method is described in JP-A No. 61-42520, Macromolekol Vol. 18, p. 825 (1985), etc. Are listed.

As for the molecular weight of the polymer of the present invention, any number-average molecular weight measured by GPC in terms of polystyrene can be preferably used if it is 1,000 or more and 500,000 or less, but especially 100,000 or more and 500,000 or less can be used.
0 to 100,000 is preferable.

The metal salts of the present invention include sulfur lithium iodide, sodium bromide, sodium chloride, sodium diocionate,
Examples include alkali metal salts such as potassium diocyanate, sodium perchlorate, lithium perchlorate, sodium boron tetrafluoride, rubidium thiocyanate, rubidium iodide, and mercury chloride, but hydrohalic acid, thiocyanic acid, nitric acid , 5A acid, phosphoric acid, halogen oxyacid, perhalogen oxyacid, tetrahalogenoboric acid, or hexahalogenated phosphoric acid.

The amount of the metal salt of the present invention added is 0.01 to 1.0 equivalent, preferably 0.02 to 0.5 equivalent per monomer such as ethylene oxide unit or ethyleneimine unit in the polymer.
It's a hit. That is, if the amount is less than 0.01 equivalent, it is difficult to obtain a high electrical conductivity, and the complex formation of the polymer of the present invention becomes insufficient, and if the amount exceeds 1 equivalent, it is difficult to uniformly dissolve the polymer.

To add and dissolve the metal salt of the invention into the polymer of the invention, add the metal salt directly to the polymer and, if necessary,
Although it is possible to dissolve the metal salt by stirring, the metal salt is dissolved in a polar solvent such as methanol, ethanol, methoxyethylene glycol, dimethylbormamide, dimethyl sulfoxide, water, etc., and then the polymer is added to form a homogeneous solution. A method of doing so is preferred.

By applying and drying the uniform solution prepared in this manner, the layer having antistatic properties of the present invention (hereinafter referred to as antistatic layer for convenience) is formed.

The application amount of the polymer of the present invention is 8 to 500 mg/v'
, particularly preferably 10 to 3001110/v'.

In the silver halide photographic photosensitive material of the present invention, the layer containing the polymer complex having ion conductivity can be coated on either side of the support, but in order to obtain a good antistatic effect, In particular, it is preferable to apply it to the batching layer.

Supports of the present invention include paper laminated with α-olefin polymers (e.g., polyethylene, polypropylene, ethylene/butene copolymers, etc.), synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, etc. , polycarbonate, polyamide, and other plastic films.

In the present invention, for example, in order to improve the physical properties of the film, a hydrophobic polymer soluble in the coating solvent may be added to the extent that a uniform coating film can be formed.

Such hydrophobic polymers include cellulose esters such as cellulose acetate and cellulose diacetate;
Examples include polystyrene, polymethyl methacrylate, polyvinyl acetate, cellulose ether, etc.
Particularly preferred are cellulose esters.

In the silver halide photographic material of the present invention, a single layer of hydrophobic polymer may be provided on the antistatic layer of the present invention as an overlay layer.

At this time, the amount of the hydrophobic polymer added is preferably 50% by weight or less based on the polymer of the present invention.

Furthermore, a single layer of hydrophobic polymer is provided on the antistatic layer of the present invention.
The amount of hydrophobic polymer applied is 50 to 500 m
q/f.

The antistatic layer of the present invention may optionally contain a known matting agent,
It can contain a slip agent, a surfactant, colloidal silica, etc.

Pine 1~ agents include silicon oxide, aluminum oxide, magnesium oxide, and other oxides with a particle size of 0.01 to 0.5μ, polymethyl methacrylate with a particle size of 0.1 to 5.0μ, High molecular compounds such as methyl methacrylate and methacrylic acid copolymers can be used.

As the slip agent, phosphate ester of higher alcohol having 8 to 22 carbon atoms or its amine salt, valmitic acid,
Stearic acid, behenic acid, etc., and silicones can be used.

As the surfactant, fluorine-based surfactants are particularly suitable. Additionally, additives such as antihalation dyes may be added depending on various purposes.

The silver halide photographic material of the present invention is a conventional black-and-white silver halide photographic material (for example, a black-and-white photographic material, a black-and-white photographic material for X-ray, a black-and-white photographic material for printing, etc.), a conventional multilayer color photographic material, etc. Materials (e.g. color reversal film, color negative film, color positive film, etc.)
It can be used as a variety of silver halide photosensitive materials. This is particularly effective when used as a silver halide photosensitive material for high-temperature rapid processing or a high-sensitivity silver halide photosensitive material.

The silver halide emulsion of the silver halide photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride as silver halides. Any material used in ordinary silver halide emulsions can be used, but silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or they may be grown after seed particles are created. The method of making and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling pH 11)A(I) in a mixing pot.This method By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size are obtained.A conversion method may be used at any step in the formation of silver halide to change the halogen composition of the grains.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

Silver halide grains contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts during the grain formation and/or growth process. By adding metal ions using at least one selected from (including complex salts), these metal elements can be contained inside the particles and/or on the particle surface, and by placing them in an appropriate reducing atmosphere. , reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure
Closure (hereinafter abbreviated as RD)) No. 17643, Section 2 can be carried out.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 01 to 20μ can be used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is below 0.20 D. Here, the grain size is the diameter in the case of spherical silver halide, and the diameter in the case of spherical grains other than spherical. This indicates the diameter when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
Negative metal sensitization methods using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that does not itself have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, boropolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used. .

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

As a binder (or protective colloid) for silver halide emulsions, it is best to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, monomers, etc. Hydrophilic colloids such as synthetic hydrophilic polymeric substances such as mono- or copolymers, and polymer latexes such as polyethyl acrylate can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention using a silver halide emulsion contain one or two hardeners that cross binder (or protective colloid) molecules and increase film strength. By using the above, hardening can be achieved. The hardening agent can be added in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing liquid.

It is also possible to add a hardening agent therein.

Examples of hardening agents include aldehydes (bormaldehyde, glyoxal, geltaraldehyde, etc.), N
-Medylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (2,3
-dihydroxydioquilene, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-3-
triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-
〇-Hydroxy-5-t-riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.)
, etc. can be used alone or in combination.

A plasticizer may be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention for the purpose of increasing flexibility. A preferred plasticizer is R.D.
This is a compound described in A of Section X■ of No. 17643.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

In the emulsion layer for each light-sensitive phase of the present invention, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. A dye-forming coupler that forms is used.

The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's light-sensitive spectrum, and for the blue-sensitive silver halide emulsion layer to form a yellow dye-forming dye. A magenta dye-forming coupler is used in the green-sensitive silver halide emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive silver halide emulsion layer. However, depending on the purpose, a silver halide color photographic material may be produced using a different combination from the above combination.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either equivalence is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DrR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction in the makuuchi separated by the coupling reaction. DIR couplers, and timing DIR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. Colorless couplers that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes (also referred to as competitive couplers) can also be used in conjunction with dye-forming couplers.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Yellow dye-forming couplers that can be used include, for example, U.S. Pat.
, 875,057, 3.265.506, 3.408.194, 3,551.155M, 3,582,322, 3,725,072,
No. 3.891.445, West German Patent No. 1,547,86
No. 8, West German Application No. 2,219,917, No. 2,26
No. 1,361, No. 2,414.00.6 @, British Patent No. 1,425,020, Special Publication No. 10783/1983,
JP-A-47-26133, JP-A No. 4g-73147, JP-A No. 50-634.1, JP-A No. 50-87650, JP-A No. 50-
No. 123342, No. 50-130442, No. 51-2
No. 1827, No. 51-102636, No. 52-82
No. 424, No. 52-115219, No. 5g-9534
Examples include those described in No. 6, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Examples of magenta color-forming couplers that can be used include, for example, U.S. Pat. No. 2,600.788, U.S. Pat.
No. 3.311゜416, No. 3,419,39
No. 1, No. 3,519,429, No. 3.558.3
No. 19, No. 3.582.322, No. 3,615.
No. 506, No. 3.834.908, No. 3.891
, No. 445, West German Patent No. 1,810,464, West German Patent Application (OL S) No. 2, 408.665, No. 2
, No. 417,945, No. 2.418.959, No. 2
．． 424.467, JP 40-6031, JP 49-74027, JP 49-74.028, JP 4
．． No. 9-129538, No. 50-60233, No. 5
No. 0-159336, No. 51-20826, No. 51-
No. 26541, No. 52-42121, No. 52-589
No. 22, No. 53-55122, patent application No. 55-1109
Examples include those described in No. 43 and the like.

As cyan dye-forming couplers, phenol or cuff couplers are generally used. Examples of cyan couplers that can be used include U.S. Patent Nos. 2 and 4.
No. 23,730, No. 2,474,293, No. 2,
No. 801,171, No. 2.895.826, No. 3
, No. 476.563, No. 3,737,326, No. 3.758.308, No. 3.893.044, JP-A-47-37425, No. 50-10135, No. No. 50-25228, No. 50-112038,
Couplers such as those described in JP-A-50-117422 and JP-A-50-130441, and the couplers described in JP-A-58-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent as necessary, and stir with a surfactant in a hydrophilic binder such as an aqueous gelatin solution.
It may be emulsified and dispersed using a dispersing means such as a homogenizer, colloid mill, flow mixer, ultrasonic device, etc., and then added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

High boiling point solvents include phenol derivatives that do not react with the oxidized form of the developing agent, phthalic acid alkyl esters (e.g. dibutyl phthalate), phosphoric acid esters (e.g. tricresyl phosphate), citric acid esters, benzoic acid esters, alkylamides, fatty acid esters. An organic solvent having a boiling point of 150° C. or higher, such as trimesic acid ester or the like, is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, dichloroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the light-sensitive material of the present invention, causing color turbidity and deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

The silver halide photographic material of the present invention may contain an image stabilizer that prevents deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.・Protective layer of photosensitive material,
A hydrophilic colloid layer such as an intermediate layer may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent deterioration of images due to ultraviolet rays.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When the hydrophilic colloid layer of the photosensitive material contains a dye and an ultraviolet absorber, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change visibility, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the photosensitive IN. Compounds that can be preferably used as visual enhancers include RD 1
The compound is a compound described in Section XXI B to D of No. 7643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used for image promotion and other purposes.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section V of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate. and polymers and copolymers thereof. The particle size of the matting agent is preferably 0.05μ to 10μ. The amount added is preferably 1 to 3001110/y'.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 XI.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating properties improvement, antistatic property, slipperiness improvement, emulsification dispersion, adhesion prevention, photographic properties (development acceleration, film hardening, Various surfactants can be used for the purpose of improving (sensitization, etc.).

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of the surfactant include, but are not particularly limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type, glycerin type, and glycidol type,
Contains higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, cationic surfactants such as phosphoniums or sulfoniums, and acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, and phosphoric esters. Ampholytic surfactants such as anionic surfactants, amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols may be added. It is also possible to use fluorosurfactants for the same purpose.

[Effects of the Invention] In the silver halide photographic light-sensitive material of the present invention, since the polymer complex according to the present invention has ionic conductivity,
The layer containing the polymer complex has good charging properties.

Further, since the layer containing the polymer complex according to the present invention can be applied without using a binder such as a hydrophilic colloid or latex, it is formed as a uniform coating film. Therefore, the silver halide photographic material of the present invention has sufficient antistatic performance even at low humidity.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited thereto.

Example 1 A subbing layer was provided on one side of a cellulose triacetate support, and photographic constituent layers having the following layer structure were sequentially coated thereon from the support side, and on the other side of the support, a subbing layer having the following composition was applied. A backing layer having antistatic properties was prepared by applying a coating solution to a layer thickness of 50 v2/Q to prepare a silver halide photographic light-sensitive material sample of this example.

The layer structure of the photographic constituent layers used in this example is as follows.

First layer: antihalation layer (HC-1>gelatin layer containing black colloidal silver).

Gelatin 2.29/n' 2nd layer; middle layer (1, L,) 2.5-di-t-octyl hydroxide A gelatin layer containing an emulsified dispersion of non-alcoholic acid.

Gelatin 1.2 (1/*' Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL-1) average grain size (r) 0.30 μm, AO3ri containing 16 mol% Dispersed emulsion (emulsion processing)... Silver mold cloth m 1.80/l' Sensitizing dye ■... 5x10-5 mol sensitizing dye per 1 mol of silver ■... ... 1.0 x 10-5 mole cyan coupler (C-1>...006 mole colored cyan coupler (CC-1) per mole of silver per mole of silver)... Silver 0.003 mol DIR compound (D-1) per 1 mol DIR compound (D-2) 0.0015 mol per mol silver DIR compound (D-2) 0.0015 mol per mol silver 0.002 mol gelatin L4 g/f 4th layer; High sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size (r) 0.5 μm, ACl T
Monodispersed emulsion (emulsion ■) consisting of A (IBrl) containing 7.0 mol%... Silver coating amount 1.3 (1/l') Sensitized image element...... 1 mol of silver 3 x 10-5 mol sensitizing dye ■... 1.0 x 10-5 mol cyan coupler (C-1)... 0.02 per mol silver Mol colored cyan coupler (CC-1) 0,0015 mol DIR per 1 mol of silver
Compound (D-2>... o, ooi mole gelatin per mole of silver 1.0 (1'/1' 5th layer; intermediate layer N, L,) Same as second layer, gelatin layer.

Gelatin 1.0 (] /f 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion = ■... Coated silver amount 1.5 g/yt Sensitizing dye ■... ... 2.5 x 10' mol sensitizing dye IV for 1 mol of silver... 1.2 x 10-5 mol magenta coupler (M-1) for 1 mol of silver...Silver 0.05 per mole
0 mol colored magenta coupler (CM-1)...0.009 mol DIR compound <D-1> per 1 mol of silver
・・・・・・ 0.0010 mol to 1 mol of silver DIR compound (D-3) ・・・ 0.0030 mol to 1 mol of silver Gelatin 2.0 (+/'I11' 7 layers: Highly sensitive green-sensitive silver halide emulsion layer (GH-1) Emulsion -■・・・・・・-Amount of coated silver 1.4q/v" Sensitizing dye■・・・・・・'!!41 mol 1.5 x 10-5 mol sensitizing dye IV for 1 mol of silver 1.oxio-!5 mol magenta coupler (M-1) 1.5 x 10-5 mol for 1 mol of silver Te 0.0
20 mol colored magenta coupler (CM-1)...0.002 mol DIR compound (D-3>
・・・・・・ 0.0010 mol gelatin 1 for 1 mol silver, 8 g/11? 8th layer: Yellow filter single layer (YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.5 (1/v2 9th layer: low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) monodisperse emulsion consisting of A (lBrI) with an average grain size of 0.48 μm and containing 6 mol% of AU I ( Emulsion ■)... Silver coating amount 0.9 (]/l' Sensitizing dye V... 1.3 x 10-5 mol Yellow Cuff 7 per 1 mol silver
-(Y-1)...0.29 mol gelatin per mol silver 1.9(]/T, l' 10th layer: High sensitivity blue sensitive emulsion layer (BH-1) average grain Diameter 0
．． 8 μm, AaBr containing 15 mol% A(]T
Monodisperse emulsion (emulsion ■) consisting of l... Silver coating amount 0.5 (]/1' Sensitizing dye ■... 1.0 x 10-5 mol yellow per mol silver Coupler (Y-1)...0.08 mol per 1 mol of silver.

DIR compound (D-2)... 0.0015 mol gelatin per 1 mol silver 1.6 (]/1' 11th layer; 1st protective layer (Pro-1) Silver iodobromide ( ΔQ11 mol% average particle size 0.07 μm) Silver coating amount 0.50/i' Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

Gelatin 1.2! J/f 12th layer; second protective layer (Pro-2) polymethyl methacrylate particles (diameter 1.5 μm), ethyl methacrylate: methyl methacrylate: methacrylic acid copolymer particles (average particle size 25 μm), and formalin Gelatin layer containing scavenger (H8-1>) Gelatin 1.2 (] /f Organopolysiloxane 500 mq /v'Organofluoro compound F-1 20 mO/w' In each layer, gelatin hardening agent (H-1) and gelatin 3
0% by weight polyethyl acrylate latex surfactant was added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye ■: Anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; Anhydro 9-ethyl-3,3'-di (
3-sulfopropyl)-4,5,4',5'-dibenzodialulpocyanine hydroxide sensitizing dye Rubocyanine hydroxide sensitizing dye Iv: Anhydro 9-ethyl-3,3'-di(3-sulfopropyl)-5,6.5',6'-dibenzoxacarbocyanine hydroxide sensitizing dye ■: Anhydro 3, 3'-di(3-sulfopropyl)-4.5-benzo-5'-mel~xythiacyanine and below margin C-] C-I H SaH3 CM-1,C/ UV-2 1-I S -1 ShiH-] F~1 Ca F17S ( ) + NCH2C00K The composition of the conductive coating liquid used in this example is shown below.

(Additional amount) 1. Polymer of the present invention described in Table 1 below x g2, Metal salt of the present invention described in Table 1 below yg3, Acetone
600 dai 4, methanol
4001g However, in Sample No. 11 for comparison used in this example, instead of the polymer of the present invention and the metal salt of the present invention, U.S. Patent No. 4.54.2,
According to the method described in Example 1 of No. 095, a coating liquid in which a nonionic surfactant having a polyethylene oxide chain and an alkali metal salt were dispersed in the latex shown below was used, and in sample No. 012 for comparison, Unexamined Japanese Patent Publication 1973
A coating liquid prepared using the following ionene-type polymer according to the method described in Example 3 of No.-92125 was used.

For the samples thus obtained, the relative humidity was 50%.
(RH), 20% (RH)
Measurement was performed at 25°C using a Keithley picoammeter based on TM Standard 1')-257.

In addition, after conditioning the humidity of an unexposed sample at 25°C and 25% RH for 2 hours, the sample was rubbed with a neoprene rubber roller with the emulsion side facing down in a dark room under the same air conditioning conditions, and then developed with the following processing solution. , bleaching, fixing, washing and stabilization were performed to examine the degree of static mark occurrence.

The results are shown in Table 1 below.

In addition, the evaluation of the degree of static mark occurrence was as follows: A: No static marks were observed at all. B: Some static marks were observed. C: A considerable amount of static marks were observed. D: No static marks were observed. It was divided into four stages, which were almost universally recognized.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 3 minutes 15 seconds Fix
Washing with water for 6 minutes and 30 seconds Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Colored image i12] 4-amino-3-methyl-N-ethyl-N-(β-didroxyethyl) -aniline sulfate 475Q anhydrous sodium sulfite 425g hydroxylamine 1/2 sulfate 2. OQ anhydrous potassium carbonate
37.5 (sodium monobromide
1.3g ditritriacetic acid trisodium salt (monohydrate) 2.59゛
Potassium hydroxide 1.0 g Add water to bring the volume to 1.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt ioo, o g Ethylenediaminetetraacetic acid diammonium salt 10.0 (] Ammonium bromide 150.0 (1 glacial acetic acid 10.0d Add water to make 1 fl, use ammonia water Adjust to ρl1-6.0.

[Fixer] Ammonium diosulfate 175.0 g Anhydrous sodium sulfite 8.50 Sodium metasulfite 2.3 g Add water to 11
and adjust the pH to 6.0 using acetic acid.

Stabilizing solution 1 Formalin (37% aqueous solution) 1.5 d Konidax (manufactured by Konishiroku Photo Industries Co., Ltd.) 7.5 ml Add water to make a powder.

The following margins are: Latex H3 disclosed in U.S. Pat. (The surface resistivities of Samples No. 31 to No. 10 are smaller than those of the comparative examples (Samples No. 11 and No. 12). The samples according to the present invention have good charging properties. Especially at low humidity (20% RH), this effect is remarkable.

This is also confirmed by the fact that no static marks were observed in the sample according to the present invention in the test of this example.

Example 2 An overcoat layer having the following composition was coated on the backing layer of the sample obtained in Example 1, and the same test as in Example 1 was conducted.

1. Cellulose diacetate 5g2, acetone 600d3, methanol 400vQ4, silica fine particles 2g (average particle size 0.2μ
m) 5, stearic acid 2g6, fluorine-based graft polymer 〇, 5g (Aron G
(manufactured by Toagosei Kagaku Co., Ltd.) The above coating composition was overcoated at a ratio of 5512/l.

The results are shown in Table 2 below.

As is clear from the results in Table 2 above, the silver halide photographic light-sensitive material of this example, which has a layer structure that further has an overcoat layer on the backing layer, which is an antistatic layer, also has the effects of the present invention. Qin in the same way.

Example 3 A subbing layer was provided on a polyethylene terephthalate support,
On top of that, photographic constituent layers having the following layer structure are sequentially applied,
On the other side of the support, a conductive coating liquid having the following composition was applied to a layer thickness of 50 v'/Q to prepare a sample of the indirect X-ray photosensitive material of this example.

It should be noted that the amounts of additives other than silver halide are shown per mole of silver halide unless otherwise specified.

1st layer: Antihalation layer Dye (I) 31n<1/1' Gelatin 0.20/m' 2nd layer: Emulsion layer average grain size 1.2μ, color enhanced with sensitizing dye (I), (II> An emulsion-coated silver plate consisting of 8 g Br containing 1.5 mol % of A(] r 4 g/v24-hydroxy-6-methyl-1,3,3a,7-titrazaindene 1.2 g diethylene glycol 11.0 ( 1 para-nitrophenyl triphenyl phosphite chloride 0.2 g Gelatin 2.5 (]]/m2 polyethyl acrylate]-latex 10 (1/,' 3rd layer; protective layer Sodium diethylhexyl succinate sulfonate 0. 015 g/l' glyoxal 0.02 (1/1' mucochloric acid
0.015 (1/12 polymethyl methacrylate particles (average particle size 3-4μ) 50 m (1/v2 polyethyl acrylate latex 0.5 (1/12 gelatin 0.4 g/i' organic fluoro compound 600 Fl (+ /TI?Ca F17SO2N
CH2GOOK Dye 1 (■) SO3Na, SO3Na O3Na sensitized color background dye (II) * -COOC2H9 The composition of the conductive coating liquid used in this example is shown below.

(Additional amount) 1. Polymer of the present invention described in Table 1 below xg2, Metal salt of the present invention described in Table 1 below y93, Resorcinol
1g3, acetone
600g 4, methanol
The same test as in Example 1 was conducted on 400 X-ray photosensitive material samples.

The processing performed in this example is as follows.

[Processing step 1 Development 30℃ 4
Fix for 5 seconds at 25℃
Wash with water for 35 seconds at 15℃
Dry for 35 seconds at 45℃
20 seconds [Developer] [Fixer] (Part A) (Part B) When using Part A: 275d, Part B: 40t
Add water to J2 to make 1 g.

As is clear from the results in Table 3 above, the antistatic effect of the present invention can be similarly obtained in the indirect X-ray photosensitive material F8I-.

Claims (1)

[Claims] 1. A silver halide photographic material comprising at least one layer containing an ion-conducting polymer complex on a support.