JPS62275245A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having excellent anistatic property by incorporating a non-ionic surface active agent, an anionic surface active agent having polyoxyethylene group and a specific salt to a hydrophilic colloidal layer. CONSTITUTION:The titled material contains at least one kind of the non-ionic surface active agent, at least one kind of the anionic surface active agent having polyoxyethylene group and at least one kind of the salt shown by formula I-IV in at least a hydrophilic colloidal layer. In the formula, M is an alkali metal, an alkaline earth metal and NH4, (l) is 1, if M is the alkali metal or NH4 group, (l) is 2, if M is the alkaline earth metal. (n) and (m) are each an integer of satisfying the following formula, namely n=2n+p (wherein p is 1 or -1 or -3). The non-ionic surface active agent and the anionic surface active agent are more preferably those similar to the compds. shown by the formulas A and B.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention has excellent antistatic properties, does not adversely affect photographic properties, and also prevents contamination of the processing solution in automatic processors. This invention relates to a silver halide photographic material that does not cause troubles (uneven drying, film staining, etc.) due to the adhesion of water-insoluble substances to conveyance rollers or the generation of water-insoluble substances.

[Conventional technology]

Photographic materials generally consist of an electrically insulating support and a photographic layer. Electrostatic charges often build up. This accumulated electrostatic charge causes many problems, but the most serious problem is that the photosensitive emulsion layer is exposed to light by discharging the accumulated electrostatic charge before processing, and when the photographic film is processed. It causes dotted spots (spotted spots) or dendritic or feather-like streaks. This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, or in some cases completely destroys it.

For example, if it appears on a medical or industrial X-ray film, it will lead to a very dangerous judgment.

Furthermore, when it appears on color film, microfilm, etc., it leads to loss of image information.

As mentioned above, such static loads are often accumulated during the production and use of photographic materials. This occurs due to separation of the support surface and emulsion surface, etc. In addition, in the finished product, separation between the base blindness and the emulsion surface occurs when the photographic film is wound and changed, or between mechanical parts or fluorescence enhancement in an automatic X-ray film camera. This occurs due to contact separation, etc.

It can also occur due to contact with other packaging materials. Static marks on photographic materials induced by such accumulation of electrostatic charges become more noticeable as the sensitivity of photographic materials increases and processing speed increases. Particularly in recent years, static marks have become more likely to occur due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed side shadowing, and high-speed automatic processing. .

The best way to eliminate these electrostatic disturbances is to increase the electrical conductivity of the material so that the electrostatic charge can be quickly dissipated before the accumulated charge is discharged.

Therefore, methods of improving the conductivity of supports and various coated surface layers of photographic light-sensitive materials have been considered, and attempts have been made to utilize various hygroscopic substances, water-soluble inorganic salts, certain types of polymers, and the like. For example, U.S. Patent Nos. 2.882.157, 2,972.535, 3,062.785,
3,262.807, 3,514,291, 3,615.531, 3,753.716, 3
, 938.999, and colloidal silica as described, for example, in US Pat. No. 3,525.621.

However, many of these materials exhibit specificities depending on the type of film support and photographic composition, giving good results for certain film supports and photographic emulsions and other photographic components, but not for other different films. Not only are supports and photographic components completely useless for antistatic purposes, but photographic properties may also be adversely affected. More importantly, the electrical conductivity of many of these substances is dependent on humidity, and they have a major drawback in that they lose their function as electrically conductive layers under low humidity conditions.

Also, JP-A-53-29715 and JP-A-60-76741
The issue describes a photographic material containing a specific anionic surfactant and a polyoxyethylene nonionic surfactant. Although it has good antistatic properties, it has not been possible to completely eliminate the occurrence of contamination of the developing processing solution, conveyance roller, etc.

It is known that it is effective to use fluorine-containing surfactants to prevent electrostatic charges on materials that do not have a polyoxyethylene group, such as neoprene rubber. Fluorine-containing surfactants are disclosed in Japanese Unexamined Patent Application Publication No. 5
3-29715 and 60-76741, and fluorine-containing surfactants containing polyoxyethylene groups do not inhibit conductivity or are self-containing. However, it is inevitable that the antistatic performance will fluctuate due to changes in temperature and humidity over time, and that the processing liquid and conveyance equipment will be contaminated.

[Purpose of the invention]

The first object of the present invention is to provide a photographic material with excellent antistatic properties, and the second object is to provide a photographic material that is free from static marks.
The third object is to provide a photographic material free from contamination of a processing solution.

[Structure and operation of the invention]

The above object is to provide at least one nonionic surfactant and at least one polyoxyethylene group in at least IN hydrophilic colloid in a photographic light-sensitive material having at least one layer containing a silver halide emulsion on a support. and one type of anionic surfactant having the following general formula (I)
This was achieved by using a photographic material containing at least one salt represented by ~(rV).

General formula (I) M (BF4.)
General formula (II) Gate (PF6) General formula (I
[[) (C, IF, COCoo) 1 general formula (rV
) (CIIF, 5O3)J? ! In the formula, M represents an alkali metal, an alkaline earth metal and NH4, l
represents 1 when M is an alkali metal or NH4, and represents 2 when M is an alkaline earth metal.

Also, n and m are m=2n+p (p is 1 or -1 or -
represents a positive integer that satisfies (represents 3).

As the nonionic surfactant used in the present invention, it is preferable to use the compounds described in JP-A-60-76741 (pages 267 to 273). Among these, particularly preferred compounds are those similar to the compounds shown below.

1, C+tHz3COO-+-CHzCHzO)+
aH2, C+Jzs (CHzC)IzO)q
HshiHko7, C3°Fz+-+-CHzCHzO→]1CIaF
z+8. Cl2F25C112CI (20(C)1
2c) +20)Is)I* -(HzCHzO)zs
H The anionic surfactant having a polyoxyethylene group used in the present invention is described in JP-A-60-76741 (27
It is preferable to use those described in (pages 3 and 274). Among these, particularly preferred compounds are those similar to the compounds shown below.

A, Ca1l+J (CH2CH20)2 (C
Hz)4sO3NaNa to NaSO2C)IO(CHzC)lzO)a
-CsllzCH20(CHzCHzO)6 C6HI
:1t, Cl zHtss −(CHtCHzO)
2 (CHz) 4sOJa general formula (I), (n
), (I[[), and the ratio of the salt represented by (IV) to the binder is 0.02:1 to 4:1 by weight, preferably o, os: 1 to 3:l, especially Preferably 0.1:
The ratio is 1 to 2:1.

The amount of salt used in the present invention is preferably 1 to 1,000 mg per square meter of photographic material.
mg is particularly preferred.

Next, examples of salt compounds according to the present invention will be shown, but the present invention is not limited thereto.

L+BF*, KBF4. CsBF4. Ca(BFt)
z, NaBF, KPF&IRbPFi, Mg
(PFa)z, Ba(PFa)z, CF3CO0Na,
CF3CO0K.

C4F4GOON+(4, (CFzCOO)tBa,
CFz=CFCOOK, CFzSQJ.

CF3CO0Na+ CJ+sSO:+Li The nonionic surfactant used in the present invention can impart conductivity in a small amount by using a salt according to the present invention as exemplified above together with an anionic surfactant having a polyoxyethylene group. In addition, it is possible to provide good antistatic performance to materials such as rubber, which makes them difficult to charge, making it possible for the first time to provide very good antistatic properties without contaminating the conveying device.

In addition, the antistatic performance changes over time and with changes in temperature and humidity are much smaller and superior to the case where a conventional fluorine-containing surfactant is used instead of the salt according to the present invention.

The amount of nonionic surfactant used in the present invention may generally be 1 to 500 mg per 11 of the photographic material, and preferably 3 to 150 IIIg.

The anionic surfactant having a polyoxyethylene group used in the present invention can be used in the same amount as the nonionic surfactant, but in order to improve antistatic performance, it is preferable to use a nonionic surfactant. The amount of anionic surfactant having a polyoxyethylene group used is a weight ratio of nonionic surfactant:anionic surfactant of 25:
The ratio is preferably from 75 to 98:2, more preferably from 60:40 to 90:10.

More preferably, carboxylic acid, sulfonic acid, phosphoric acid,
When an anionic surfactant that does not have a polyoxyethylene group such as a sulfate ester is used in combination, the cloud point of a coating liquid containing a nonionic surfactant is 8% by weight, and the cloud point is 50. The temperature is preferably 69°C or higher, more preferably 69°C or higher.

In addition, the amount of the above-mentioned anionic surfactant not having a polyoxyethylene group to be used is based on the weight ratio of the nonionic surfactant to the anionic surfactant not having a polyoxyethylene group. , 5:95-5
A range of 0:50 is preferable.

By using an anionic surfactant that does not have a polyoxyethylene group, it is possible to reduce the amount of nonionic surfactant that contaminates the developer and bleeds onto the film surface. However, even if the nonionic surfactant and the anionic surfactant are not added to the same layer, contamination and the like can be similarly prevented by changing their relative amounts.

As the binder used in the present invention, either a hydrophilic binder or a hydrophobic binder can be used.

As the hydrophilic binder, a hydrophilic natural or synthetic polymer capable of forming a film is used.

For example, proteins such as gelatin, albumin, and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; agar, sodium alginate, and hydrophilic colloids containing sugar derivatives such as starch derivatives, such as polyvinyl alcohol, acrylic acid copolymers, or these. Derivatives of esters, partial hydrolysates of these esters, vinyl copolymers such as acrylic esters, and synthetic resins thereof are used. Polyacrylic acid and polyacrylic ester derivatives are also used. can do..

Among these, gelatin is preferably used, but examples of gelatin include so-called lime-treated gelatin, acid-treated gelatin,
Any gelatin commonly used in the art, such as enzyme-treated gelatin, gelatin derivatives, and modified gelatin, can be used.

Furthermore, 4 components with an average molecular weight of 100,000 or less
It is most preferred to use gelatin containing 0 wt% or less.

The average molecular weight here is the weight average molecular weight measured by gel permeation chromatography (hereinafter referred to as r'GPC method).

An example of the conditions for the GPC method is shown below.

■ Column: Sepharose CL4B (Pharmacia
(manufactured by Fine Chemical Co.) Length 80cm 5T-35℃, φ151 ■Separated liquid: 0.2M CHs COOH/0
．． 2MCHx COON a aqueous solution flow rate 0.29 n1/+nm, Verister pump (manufactured by ATTO) ■ Detector: Ultraviolet absorption spectrophotometer (UV: wavelength 254n)
m) ■Analytical sample: Gelatin with an absolute amount of 25 mg To calculate the percentage value of components with an average molecular weight of 100°OOO or less from a chart obtained by GPC, the α component (ζ average molecular weight 10
A line perpendicular to the baseline is drawn from the peak position obtained for 0,000), and the ratio of the area of the area to the right of the perpendicular line (low molecular weight portion) to the total area is calculated.

As the hydrophobic binder, various hydrophobic polymers having film-forming ability can be used. For example, 7-acrylate copolymers, methacrylate copolymers, styrene/
Butadiene copolymers, acrylonitrile/butadiene copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, polyester copolymers, polyurethane copolymers, vinyl ether copolymers, vinyl esters Cellulose diacetate, cellulose triacetate, etc. can be used in the form of an organic solvent solution or an aqueous dispersion. Among these, styrene/butadiene copolymer latex or aqueous polyester copolymer (e.g. WDSIZE manufactured by Eastman Chemical Co.) or aqueous polyurethane copolymers (such as Daiichi Kogyo M-yaku (I1
Superflex 100 (manufactured by Co., Ltd.) is most preferred.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 12 mol % silver iodide.

The average grain size of silver halide grains in a photographic emulsion (the grain size is the grain diameter for spherical or approximately spherical grains, and the ear length for cubic grains, expressed as the average calculated by the projected area) is , about 0.04 μm to 5 μm, preferably about 0.2 to 2 μm gives good results.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may have a regular crystal shape such as a tetrahedron or a dodecahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or a composite of these crystal shapes. It can be something that has a shape. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface (or may be particles in which the latent image is mainly formed inside the particle).

Emulsion (The Focal Pres.
s publication, 1964), and Re5search.
Disclosure Vol, 176 (197
8゜12) I? D-17643 and the like. i.e. acid method,
Any of the neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, or the like.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the solution in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Further, the amount of these additives may be small or large depending on the intended photosensitive material.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which involves gelatinization of gelatin, may be used. A precipitation method (flocculation method) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used. The process of removing soluble salts may be omitted.

The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, e.g.
W ; Die Grundlagen
der Photogra
ischen Prozesse wit Si
lberhalogeniden (Akademisc
he Verlagsgesellschaft, 1
968) on pages 675-734 can be used.

That is, sulfur enrichment methods using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. gold salts,
Pt, Ir.

A noble metal sensitization method using complex salts of metals of group Ⅰ of the periodic table such as Pd can be used alone or in combination.

Specific examples of these include U.S. Patent No. 1 for sulfur sensitization.
, No. 574,944, No. 2,410,689, No. 2,278,947, No. 2,728,668, No. 3,656,955, etc., and U.S. Patent No. No. 2,983.609, No. 2,419,974, No. 4,054,458 No. 1 No. 2,399,083, No. 2,448, U.S. Pat.
No. 060, British Patent No. 618,061, and other specifications.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.: Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Beichi No. 2.503,776, Beichi No. 3.459.553, Beichi No. 3
, No. 177.210, Research Disclosure (
Research Disclosure) Volume 176 1
7643 (issued December 1978), Section 23, Section IV, Section 3, etc.

The aggravating dye used in the present invention is used at a concentration equivalent to that used in ordinary negative halogen and silveride emulsions. It is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. x 10 i mol, especially 1 sensitizing dye per mol of silver halide, about 4 x 1
It is preferred to use a concentration of 0-' to 1X10-3 molar.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); Meilecaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes, For example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid Many compounds known as antifoggants or stabilizers can be added, such as amides and the like.

For more information, see E. J. Birr, r 5tabi.
lization of Photographic 5
river Halide Emulzlons J(
Focal Press, 1974).

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic agents, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, Various surfactants may be included for various purposes such as contrast enhancement, exacerbation, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids;
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides; heterocycles such as alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidabrilam, etc. Cationic surfactants such as quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary Ammonium salt compounds, urethane salts,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.)
, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-5-)riazine, 1°3-vinylsulfonyl-2-propatol, etc.), active halogens Compounds (2,4-dichloro-6-hydroxy-5-)riazine, etc.), muco)rogenic acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer 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 photographic light-sensitive material of the present invention, the silver halide emulsion layer may be provided not only on one side but also on both sides of the support.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above.

Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention. An example of a matting agent is water such as polymethyl methacrylate with a suitable particle size (preferably a particle size of 0.3 to 5 μm or a particle size of at least 2 times, especially 4 times or more, the thickness of the protective layer). Organic compounds such as dispersible vinyl polymers or inorganic compounds such as silver halide, strontium halium sulfate, etc. are preferably used. Smoothing agents help prevent adhesion failure similar to matting agents, and are particularly effective in improving the frictional properties of motion picture films related to projection or camera compatibility during projection; specific examples include liquid paraffin, Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or derivatives thereof, silicones such as polyalkylpolysiloxanes, polyarynubolysiloxanes, polyalkylarylpolysiloxanes, or alkylene oxide addition derivatives thereof, etc. is preferably used.

Various other additives may be used in the photographic material of the present invention, if necessary. Examples include dyes, development accelerators, fluorescent whitening agents, color antifoggants, and ultraviolet absorbers. Specifically, research disclosure (
RESEARCHDISCLO5URE) No. 176 No. 2
Those described on pages 2 to 31 (RD-17643, 1978) can be used.

The silver halide photographic material of the present invention may also be provided with an antihalation layer, an intermediate layer, a filter layer, etc., if necessary.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on one or both sides of a visible support commonly used in photographic materials. Useful as flexible supports are films consisting of semi-synthetic or synthetic follicular molecules such as cellulose sulfate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated or laminated with polyethylene, polypropylene, ethylene/butyne copolymer), etc. The support may be colored using dyes or pigments. It may be illuminated for the purpose of photosensitivity. The interface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

Specifically, silver halide photographic materials using the silver halide photographic emulsion of the present invention include X-ray sensitive materials, optical materials,
Liss photosensitive materials, black and white photography photosensitive materials, color negative photosensitive materials, color reversal photosensitive materials, color photographic paper, colloid transfer process, silver salt diffusion transfer process, Gui transfer process, silver dye bleaching method, printout photosensitive materials, heat development It can be used for photosensitive materials, etc.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Fluorescent lamps, mercury lamps, xenon arc lamps, carbon mark lamps, xenon flash lamps, cathode ray tube flying spots, light emitting diodes, laser lights (e.g. gas lasers, YA
Any of various known light sources including infrared light, such as G laser, dye laser, semiconductor laser, etc., can be used. It may also be exposed to light emitted from a phosphor excited by electron beams, X-rays, T-rays, α-rays, or the like. The exposure time is 1/10, which is normally used in cameras.
Exposure time from 00 seconds to 1 second, as well as 1/1000
Exposures shorter than a second can be used, such as 1/10' to 1/106 second exposures using xenon flash lamps or cathode ray tubes, or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure
ure) No. 176, pages 28-30 (RD-17643
) Any of the known methods and known treatment liquids can be applied. Depending on the purpose, this photographic processing may be either a photographic process that forms a silver image (black and white photographic process) or a photographic process that forms a dye image (color photographic process).The processing temperature is usually 18°C.
to 50°C, but the temperature may be lower than 18°C or higher than 50°C.

In addition, other known development methods (such as thermal development) may be used depending on the case.

For example, the developer used in blank photographic processing can contain known developing agents.

As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-
phenyl-3-pyrazolidone), aminophenols (
For example, N-methyl-p-aminophenol), etc.
They can be used alone or in combination.

The developing solution generally contains other known preservatives, alkaline agents, and
Contains Hfft, anti-capri agent, etc., and may further contain solubilizing agent, color toning agent, development accelerator, surfactant, antifoaming agent, water softener, hardening agent, viscosity imparting agent, etc. .

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" development processing is a development process in which dihydroxybenzenes are usually used as a developing agent and a low sulfite ion concentration is used for the photographic reproduction of line images or the halftone dot photographic reproduction of halftone images. Refers to a developing process that is carried out contagiously (details are described in Mason, ``Photographic Ink Processing Chemistry J (1966), pages 163-165).

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing agent may contain a water-soluble aluminum salt as a hardening agent.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, which can form a color by oxidative coupling with an aromatic primary amine developer (e.g., phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. It may also contain compounds. For example, as a magenta coupler, S-pyrazolone coupler, birazolopenzimitasol coupler, cyanoacetylcoumarone coupler,
There are open class acylacetonitrile couplers, yellow couplers include acylacetamide couplers such as benzoylacetanilides, pivaloylacetanilides, etc., and cyan couplers include naphthol couplers, phenol couplers, etc. . These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion.

It may also be a colored coupler that requires expensive color correction, or a coupler that releases a development inhibitor during development (so-called D (R coupler)).

In addition to DIR couplers, there are also colorless DIR couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain a coupling compound.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., as described in U.S. Pat. ), benzophenone compounds vIJ (e.g. those described in JP-A No. 46-2784), cinnamate ester compounds (e.g.
05.805, U.S. Pat. No. 3,707,375) butadiene compounds (e.g., U.S. Pat.
No. 9) or benzoxydole compounds (such as those described in U.S. Pat. No. 3,700,455) can be used. Furthermore, U.S. Patent No. 3,499
, 762 and JP-A-54-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol i-form, and bisphenols.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g. 4-
Amino-N, N-diethyl aniline, 3-methyl-
4-amino-N,N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N- ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition to this, Photography by A. Mason
Process-ir+g Chemistry (F
ocal Press, 1966), 226-22.
9, U.S. Patent No. 2.193.015, U.S. Patent No. 2.592.3
64, JP-A No. 48-64933, etc. may be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and organic antifoggants, and anticapri agents. can include. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium +:ronhydride, 1-phenyl-3-pyrazolidone. It may also contain an auxiliary developer such as, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (■), chromium (■), and copper (II), peracids, quinones, and nitroso compounds are used.

For example, ferricyanide, dichromate, iron (I[[
) or organic complex salts of cobalt (III), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1°3-diamino-2-propatoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid. ; persulfate, permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium iron(DI) ethylenediaminetetraacetate, and ammonium iron(III) ethylenediaminetetraacetate are particularly useful. Iron ethylenediaminetetraacetate (I[
[) Complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

〔Example〕

Examples of the present invention are shown below, but it goes without saying that the present invention is not limited to these Examples.

Example 1 A 180 μm polyester support was subjected to corona discharge treatment, and the butadiene/styrene/acrylic acid ratio was 48:50.
2 (weight ratio) copolymerized latex (40 t%) 100c
c, 890 cc of distilled water, and 2,4-dichloro-614
It was dried at 0°C for 5 minutes. This treatment was performed on both sides of the support.

On one side of the support treated as described above, an ortho-enhanced X-ray silver halide emulsion (cubic AgBrI with an average grain size of 0.9 μm, where I = 3.0 mol %) was applied at a concentration of 2.5 g of silver/ A and gelatin in an amount of 1.5 g/rrf, and gelatin (in an amount of 0.7 g/m), the compounds shown in Table 1, Rudnox AM (manufactured by DuPont), 2,4-dichloro -6-hydroxy-1,
3,5-1-Ryazine sodium salt aqueous solution, formalin aqueous solution, trimethylolpropane, and polymethyl methacrylate (projected area average particle size 3.6 μm) were added and coated on both sides at a speed of 150 m/min with a slide hopper coater. A sample was obtained by drying for 2 minutes and 15 seconds.

The antistatic test for each sample was conducted using the following test method. That is, the sample prepared as described above was conditioned for 12 hours at 25°C and 20% R and H in a dark room, and then the surface was rubbed with a neoprene rubber roll under the same conditions, and then automatically Development was carried out using a developing machine GX-300 (manufactured by Konishiroku Photo Industry Co., Ltd.) and a developing solution of XD-90 (manufactured by the same company). After the treatment, the degree of static marks generated was determined.

The results are shown in Table 1. The evaluation was performed as follows.

A: No occurrence B: Less than 3% occurrence in area C: Occurrence in 3% or more and less than 10% in area, 10% or more in two areas
The sample was placed between brass electrodes with a length of 1 cm and a length of 1 Q cm, and the 1-minute value was measured using an insulation meter model TR8651 manufactured by Takeda Riken. The surface resistivity was measured under the same conditions as above and at 35℃70%R.
After 30 hours of humidity control under HO, the temperature was still 25℃20%RH.
Each sample was measured under RHO at 25°C when the humidity was conditioned for 12 hours (values shown in parentheses in the surface resistivity column of the table).

Furthermore, the degree of contamination of the treatment liquid and roller of each sample was measured as follows. That is, each sample cut into 30.5 cm x 15 cm squares was exposed uniformly to an optical density of 1.0±0.1, and then processed using an automatic processing machine (equipped with a silicone roller conveyor) (developer: Konishi). Rokusha XD-
90. Fixer: Consists of 3 baths: same XF and water washing bath)
80 sheets were processed continuously.

After thoroughly drying the water-washed squeeze roller, the degree of occurrence of streak-like density unevenness occurring at the tip of the 81st sample was examined. (The occurrence of this density unevenness is correlated with the contamination of the squeeze roller.) The degree of roller contamination was evaluated according to the following four-level criteria: A: No occurrence of QQ degree unevenness was observed.

B, ff, slight unevenness occurs.

C: Considerable unevenness of >74 degrees occurs.

D: Significant density unevenness occurs.

The results are shown in Table 1.

From Table 1, it can be seen that the samples of the present invention have good antistatic performance even when exposed to low humidity conditions and have less roller contamination.

Example 2 A sample prepared in the same manner as in Example 1 and a comparative sample using the following compounds A to C as shown in Table 2 instead of compounds (I) to (IV) according to the present invention were prepared. Example 1
It was evaluated in the same way. However, not only the surface resistivity but also the static mark determination was performed at 35℃ for each sample.
Humidity conditioned for 30 hours under 70% RH, then at 25°C and 20% RH
Data was also taken for the case where the humidity was conditioned for 2 hours, and the values are shown in parentheses in the column of antistatic ability in Table 2. The results are shown in Table 2.

Compound A (anionic surfactant not containing polyoxyethylene group) NaO+S CHC00CJ+t CH2C00CaH+ff Compound B (compound other than the salt according to the present invention) NaOzS
CHCOOCH2 (CFZCF2)2 N■ CH2C00CzCHz (CFzCFz)z )
1 Compound C (compound other than the salt according to the present invention) H (CFz
CFz) 3- CHzO(CHiCHzO) s
As Table 2 shows, the samples of the present invention (sample fish 4°10,
It can be seen that No. 14 and 15) have good antistatic ability and good roller contamination level. Furthermore, it can be seen that even more favorable results can be obtained when an anionic surfactant that does not contain a polyoxyethylene group such as Compound A is used in combination (
Sample m14.15).

Comparative sample N117.18 has a good degree of static mark generation under humidity control conditions of 25° C. and 20% RH, but is extremely deteriorated under humidity control conditions of 35° C. and 70% RH for 30 hours. In contrast, the samples of the present invention show no deterioration even under such long-term humidity conditioning conditions.

Example 3 A sample prepared in the same manner as in Example 1 and a nonionic surfactant, an anionic surfactant having a polyoxyethylene group, and an anionic surfactant not having a polyoxyethylene group were added as shown in Table 3. The samples with varying amounts were analyzed in the same manner as in Example 1. The results are shown in Table 3.

However, all antistatic ability tests are even more severe23.
(''C), the humidity was adjusted for 24 hours under the condition of 20 (%) RH, and measurements and tests were conducted under the same conditions.

The compounds newly used in this example are as shown below.

■ Na03S CHC00CH2CHC41L CHzCOOC)lzcHCtlL 2H5 As understood from Table 3, the sample 11k shown in the table
All of L19 to L33 are samples according to the present invention, and as a result of the test under the above-mentioned severe conditions, it can be said that all of them show extremely good performance (Example 1.2
(See the comparison with the data in the above example of sample Kan 4, which was also used). Among them, as detailed above, samples in which the amount of nonionic surfactant and anionic surfactant having a polyoxyethylene group used are in the range of 25:75 to 98:2 in weight ratio are 20°22,23 .24.26.28～
It can be seen that No. 33 has good antistatic ability and has a low degree of roller contamination.

In addition, the weight ratio of an anionic surfactant that does not have a polyoxyethylene group and a nonionic surfactant is 5 = 95 to 50.
: Sample NlX23.29°3 used in combination within the range of 50
It can be seen that No. 1, 32.33 shows particularly excellent results in terms of antistatic ability and roller contamination.

In the margins below, descriptions of sensitometric characteristics were omitted in each example, but the samples of the present invention showed fog.

Needless to say, the sensitivity, contrast, and maximum density were also good.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to provide a photographic material that has excellent antistatic properties and is free from static marks, and the surfactant used in the present invention does not cause contamination of the developing solution. This has the effect that there is no such thing.

Claims (1)

[Scope of Claims] 1. In a photographic light-sensitive material having at least one layer containing a silver halide emulsion on a support, at least one hydrophilic colloid layer contains at least one nonionic surfactant and at least one nonionic surfactant. 1. A silver halide photographic material comprising one kind of anionic surfactant having one kind of polyoxyethylene group and at least one kind of salt represented by the following general formulas (I) to (IV). General formula (I) M(BF_4)_l General formula (II) M(PF_6)_l General formula (III) (C_nF_mCOO)_lM General formula (
IV) (C_nF_mSO_3)_lM In the formula, M represents an alkali metal, an alkaline earth metal, and NH_4. l is M is an alkali metal or N
H_4 represents 1, and alkaline earth metal represents 2. Further, n and m represent positive integers that satisfy m=2n+p (p represents 1, -1, or -3). 2. The silver halide photographic material according to claim 1, wherein the content ratio of the nonionic surfactant to the anionic surfactant is in the range of 25:75 to 98:2 by weight.