JPH0327098B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of the Invention) The present invention relates to a silver halide photographic light-sensitive material having good antistatic properties, and particularly relates to a silver halide photographic light-sensitive material that does not adversely affect photographic properties, and that can be used in an automatic processor to prevent contamination of the processing solution or water on the conveyor roller. This invention relates to a silver halide photographic light-sensitive material that does not cause problems due to the adhesion of insoluble matter and the generation of water-insoluble matter (uneven drying, film stains, etc.), hereinafter referred to as "photographic light-sensitive material". (Prior art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so they are subject to contact friction or peeling with surfaces of the same or different materials during the manufacturing process and during use. This often results in the accumulation of electrostatic charges. This accumulated electrostatic charge causes many problems, but
The most serious problem is that the photosensitive emulsion layer becomes sensitized due to the discharge of electrostatic charges accumulated before processing, resulting in dot-like spots or dendritic or feather-like line spots when the photographic film is processed. It is something that happens. 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 in medical or industrial X-ray film, it will be easily recognized that it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. Further, these accumulated electrostatic charges may cause secondary failures such as dust adhesion to the film surface or uneven coating. As mentioned above, such electrostatic charges 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 of the base surface and emulsion surface when winding and switching photographic film is performed, or mechanical parts or fluorescent sensitization in an automatic X-ray film camera. This occurs due to contact separation between the paper and the paper. It can also occur due to contact with other packaging materials.
Static marks on photographic materials induced by such electrostatic charge accumulation become more noticeable as the sensitivity of photographic materials increases and the processing speed increases. Particularly in recent years, as photographic materials have become more sensitive and are subjected to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing, static marks are more likely to occur. ing. In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic material. However, the antistatic agents that can be used in photographic light-sensitive materials cannot be the same as those commonly used in other fields, and are subject to various restrictions specific to photographic light-sensitive materials. That is, in addition to having excellent antistatic properties, antistatic agents that can be used in photographic light-sensitive materials must not have any adverse effect on photographic properties such as sensitivity, fog, graininess, sharpness, etc. of photographic light-sensitive materials; It should not adversely affect the film strength of the photosensitive material (that is, it should not be easily damaged by friction or scratching), and it should not have an adverse effect on the adhesion resistance (i.e., the surface of the photographic material or the surface of other materials should not be affected adversely. Performance is required such as not causing the photosensitive material's processing solution to fatigue quickly, not contaminating the conveyance roller, and not reducing the adhesive strength between the constituent layers of the photosensitive material.
Application of antistatic agents to photographic materials is subject to numerous restrictions. 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, including the use of various hygroscopic substances, water-soluble inorganic salts, certain surfactants, and polymers. It has been tried. Among these, surfactants are important in terms of antistatic ability, and for example, US Pat. No. 3,082,123, US Pat.
No. 3519561, No. 3625695, West German Patent No.
No. 1552408, No. 1597472, JP-A-49-85826,
No. 53-129623, No. 54-159223, No. 48-19213
No., Special Publication No. 46-39312, No. 49-11567, No. 51-
Anionic, betaine and cationic surfactants described in No. 46755, No. 55-14417, etc., or JP-A-52-80023, West German Patent No. 1422809
No. 1422818, Australian Patent No. 54441
Nonionic surfactants are known, such as those described in No./1959. However, these materials exhibit specificity depending on the type of film support and photographic composition, giving good results for some film supports and photographic emulsions and other photographic components, but not for others. Vine film supports and photographic components offer no protection against static electricity, or
Although the antistatic properties are excellent, the sensitivity of the photographic emulsion
It is extremely difficult to apply these substances to photographic materials because they adversely affect photographic properties such as fog, graininess, and sharpness, contaminate the developing solution, and cause deposits on rollers. It was hot. Furthermore, the antistatic technology using nonionic surfactants is closely related to the coating agents used in combination.
However, although progress has certainly been made in terms of antistatic performance, they do not take into account the contamination of the developing processing solution or the contamination of the transport roller, which may cause serious film failures. It's summery. For example, it is described in Japanese Patent Publication No. 51-9610 that an ethylene oxide addition polymer of a phenol-formalin condensate has excellent antistatic properties even when used in combination with various coating agents. However, the method of the patent does not solve problems caused by contamination during the development process. In other words, the roller stains, which are thought to be caused by dry deposits on the transport rollers, are extremely bad and cause problems in terms of density unevenness on the film. In addition, JP-A No. 53-29715 describes a photographic material containing a specific anionic surfactant and a polyoxyethylene nonionic surfactant, but like the above-mentioned patent, there is a risk of contamination of the developing processing solution. It is not possible to improve film failure due to contamination or conveyance roller contamination. (Objective of the Invention) The first object of the present invention is to provide a photosensitive material which is prevented from being charged and which does not cause contamination of a developing solution or a roller. The second object is to provide a photographic material which is prevented from being charged and which does not cause contamination of the sensitive material that comes after the development process. Third, it is an object of the present invention to provide a photographic light-sensitive material which is prevented from being charged without adversely affecting photographic properties such as desensitization. The fourth object is to provide a photographic material whose antistatic properties do not change over time after manufacture. (Structure of the Invention) These objects of the present invention are to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. , at least 1
This was achieved by a silver halide photographic light-sensitive material characterized by containing various nonionic surfactants and at least one anionic surfactant having a polyoxyethylene group. Examples of the nonionic surfactant used in the present invention include compounds represented by the following general formula [-1] or [-2]. R ₂ , R ₃ , R ₇ , R ₉ are hydrogen atoms, substituted or unsubstituted alkyl groups, aryl groups, alkoxy groups,
Represents a halogen atom, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group. In the formula, R ₆ and R ₈ represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen group, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group.
In the general formula [-2], the substituents on the phenyl ring may be asymmetrical. R ₁ , R ₄ and R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group.
R ₁ and R ₅ , R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ may be linked to each other to form a substituted or unsubstituted ring. However, R ₁ and R ₅ cannot become hydrogen atoms at the same time. n ₁ , n ₂ and n ₃ are average degrees of polymerization of ethylene oxide and are numbers from 2 to 50. Moreover, m is an average degree of polymerization, and is a number from 2 to 50. R ₂ , R ₃ , R ₆ , R ₇ , R ₈ and R ₉ are preferably methyl, ethyl, i-propyl, t-butyl, t-amyl, t-hexyl, t-octyl, nonyl, decyl, dodicyl, Trichloromethyl, tribromomethyl, 1-phenylethyl, 2-phenyl-2
- Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as propyl, substituted or unsubstituted aryl group such as phenyl group, p-chlorophenyl group, -OR ₁₁ (herein, R ₁₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) Represents a substituted or unsubstituted alkyl group or aryl group (the same applies hereinafter)
A substituted or unsubstituted alkoxy group represented by, a halogen atom such as a chlorine atom, a bromine atom, or R ₂ , R ₃ ,
R ₇ and R ₉ may be hydrogen atoms. Among these, R ₆ and R ₈ are preferably an alkyl group or a halogen atom, and particularly preferably a bulky tertiary alkyl group such as a t-butyl group, a t-amyl group, or a t-octyl group. R ₇ and R ₉ are particularly preferably hydrogen atoms. That is, the compound of general formula [-2] synthesized from 2,4-disubstituted phenol is particularly preferred. R ₁ , R ₄ , R ₇ are preferably hydrogen atoms, methyl groups,
Ethyl group, n-propyl group, i-propyl group, n
- Substituted or unsubstituted alkyl groups such as heptyl group, 1-ethylamyl group, n-undecyl group, trichloromethyl group, tribromomethyl group, α-furyl group, phenyl group, naphthyl group, p-chlorophenyl group, p- It is a substituted or unsubstituted aryl group such as a methoxyphenyl group or a m-nitrophenyl group. Also, R ₁ and R ₅ , R ₄ and R ₅ , R ₆ and R ₇ and R ₈
R ₉ may be linked to each other to form a substituted or unsubstituted ring, such as a cyclohexyl ring. Among these, R ₁ , R ₄ and R ₅ are particularly preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a furyl group. n ₁ , n ₂ and n ₃ are particularly preferably numbers from 5 to 30. n ₂ and n ₃ may be the same or different. These compounds are disclosed in, for example, JP-A No. 53-29715,
Japanese Patent Publication No. 54-89626, Japanese Patent Application No. 57-85764, Japanese Patent Application No. 1987-85764
No. 57-90909, "New Surfactants" by Hiroshi Horiguchi (Sankyo Publishing, 1975), etc. Next, specific examples of nonionic surfactants preferably used in the present invention will be shown. Compound example The anionic surfactant having a polyoxyethylene group used in the present invention is represented by the general formula []. General formula [] R ₀ -A (-CH ₂ CH ₂ O) - _o4 BD In the formula, R ₀ is a substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms, and A is - O- group, -S- group, -COO- group,

【formula】

【formula】

[Formula] (where R ₁₀ represents a hydrogen atom or a substituted or unsubstituted alkyl group). B represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and D represents an anion group. Further, n ₄ is the average degree of polymerization of ethylene oxide, and is an integer of 1 to 50. As a preferable example of the general formula [], R ₀ is preferably an alkyl group, alkenyl group, or alkylaryl group having 4 to 24 carbon atoms, particularly preferably a hexyl group, dodecyl group, isostearyl group, oleyl group, or t- Butylphenyl group, 2,4-di-
t-butylphenyl group, 2,4-di-t-pentylphenyl group, p-dodicylphenyl group, m-pentadecaphenyl group, t-octylphenyl group,
They are 2,4-dinonylphenyl group, octylnaphthyl group, etc., _n4 is preferably 2 to 10, and B preferably has 1 to 6 carbon atoms. Among the alkylene groups, particularly preferred are methylene group, ethylene group, propylene group, butylene group, and the like. D is preferably -COOM, _-SO3M , -O- _SO3M ,

【formula】

[Formula]. Here, M represents an inorganic or organic cation, preferably a hydrogen atom group, an alkali metal, an alkaline earth metal, ammonium, or a lower alkylamine. These compounds are described in U.S. Patent No. 3,026,202;
No. 2600831, No. 2719087, No. 3201252, No. 2600831, No. 2719087, No. 3201252, No.
No. 3415649, JP-A-54-98235, JP-A-40-23747
British Patent No. 1178546, British Patent No. 1344987, US Patent No. 3264108, British Patent No. 2600831, etc. Specific examples of the anionic surfactant containing polyoxyethylene of the present invention are shown below.

【table】

[Table] ｜

ONa

[Table] The amount of surfactants represented by general formulas [-1], [-2], and [] varies depending on the form, type, coating method, etc. of the photographic material used, but in general, 1-1000mg per ^1m2 of
5 to 200 mg is particularly preferred. The method of applying these surfactants of the present invention into the layer of a photographic light-sensitive material is to dissolve them in water, an organic solvent such as methanol, ethanol, acetone, or a mixed solvent of water and the organic solvent, and then apply the surfactants on a support. It can be incorporated into a light-sensitive emulsion layer, a non-light-sensitive auxiliary layer (for example, a backing layer, an antihalation layer, an intermediate layer, a protective layer, etc.), or it can be sprayed, coated, or immersed in the solution on the surface of a support. Just dry it. At this time, two or more of the nonionic surfactants and anionic surfactants of the present invention may be used as a mixture. Another antistatic agent can also be used in combination with the layer containing the nonionic surfactant and anionic surfactant of the present invention or other layers, and by doing so, a more preferable antistatic effect can be obtained. Such antistatic agents include, for example, U.S. Pat.
No. 3262807, No. 3514291, No. 3615531, No.
No. 9753716, No. 3938999, No. 4070189, No. 9753716, No. 3938999, No. 4070189, No.
No. 4147550, German Patent No. 2800466, Japanese Unexamined Patent Publication No. 1973-
No. 91165, No. 48-94433, No. 49-46733, No. 50
-54672, No. 50-94053, No. 52-129520, etc., e.g.
No. 2982651, No. 3428456, No. 3457076, No.
Surfactants such as those described in US Pat. No. 3,454,625, US Pat.
Metal oxides, colloidal silica, etc., barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloidal silica or powdered silica as described in No. 3062700, No. 3245833, No. 3525621, etc. Examples include so-called matting agents consisting of the following. In addition, polyol compounds such as ethylene glycol, propylene glycol, 1,1,1-trimethylolpropane, etc. as shown in JP-A-54-89626 may be used in the layer containing the nonionic surfactant and anionic surfactant of the present invention, or in other layers. By doing so, a more preferable antistatic effect can be obtained. The nonionic surfactant of the present invention and the layer containing the nonionic surfactant include an emulsion layer, an undercoat layer on the same side as the emulsion layer, an intermediate layer, a surface protection layer, an overcoat layer, and a back layer on the opposite side to the emulsion layer. etc. Among these, surface layers such as a surface protective layer, an overcoat layer, and a back layer are particularly preferred. Examples of the support used in the photographic material of the present invention include films such as polyolefins such as polyethylene, polystyrene, cellulose derivatives such as cellulose triacetate, cellulose esters such as polyethylene terephthalate, or baryta paper, synthetic paper, or paper. Included are supports made of sheets coated on both sides with these polymer films, and the like. The support used in the present invention can also be provided with an antihalation layer. For this purpose carbon black or various dyes, e.g.
Oxole dyes, azo dyes, aryrite dyes,
Examples include styryl dyes, anthraquinone dyes, merocyanine dyes, and tri(or di)allylmethane dyes. The light-sensitive material according to the present invention includes ordinary black-and-white silver halide light-sensitive materials (for example, black-and-white light-sensitive materials for photography,
Examples include various photosensitive materials such as black-and-white photosensitive materials for X-ray, black-and-white photosensitive materials for printing, etc.), ordinary multilayer color photosensitive materials (e.g., color reversal films, color negative films, color positive films, etc.). can. In particular, the effect is great for silver halide photosensitive materials for high-temperature rapid processing and high-sensitivity silver halide photosensitive materials. Photographs of the silver halide photosensitive material according to the present invention will be briefly described below. As a binder for the photographic layer, proteins such as gelatin and casein; carboxymethyl cellulose,
Cellulose compounds such as hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, starch derivatives = synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives thereof and partially hydrated Decomposition products etc. can also be used together. Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin. In addition to replacing part or all of gelatin with synthetic polymeric substances, so-called gelatin derivatives, i.e., functional groups contained in the molecule such as amino, imino, hydroxy, or carboxyl groups, can be replaced with groups that can react with them. It may be used instead of a reagent treated or modified with one reagent, or a graft polymer to which molecules of a polymeric substance are bonded. The silver halide emulsion layer of the photographic light-sensitive material of the present invention,
Types of silver halide used in surface protective layers, manufacturing methods, chemical sensitization methods, antifoggants, stabilizers,
There are no particular restrictions on hardeners, antistatic agents, plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizing dyes, dyes, color couplers, etc.
Licensing, Vol. 92, pp. 107-110 (December 1971) and Research
Disclosure) Vol. 176, pages 22-31 (December 1978) can be referred to. In particular, antifoggants and stabilizers include 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene-3-methyl-benzothiazole,
A large number of compounds such as 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury compounds, mercapto compounds, and metal salts are used as hardeners, such as mucochloric acid, mucobromic acid, mucophenoxychloric acid, Mucophenoxybromic acid, formaldehyde, dimethylol urea,
Trimethylolmelamine, glyoxal, monomethylglyoxal, 2,3-dihydroxy-
1,4-dioxane, 2,3-dihydroxy-5
-Methyl-1,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran,
Aldehyde compounds such as glutaraldehyde;
Divinyl sulfone, methylene bismaleimide, 5
-acetyl-1,3-diacryloyl-hexahydro-s-triazine, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,
3,5-trivinylsulfonyl-hexahydro-
s-triazine bis(vinylsulfonylmethyl)
Active vinyl compounds such as ether, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane; 2,4-dichloro-6-hydroxy-s-
Triazine sodium salt, 2,4-dichloro-
6-methoxy-s-triazine, 2,4-dichloro-6-(4-sulfoanilino)-s-triazine sodium salt, 2,4-dichloro-6-(2
-sulfoethylamino)-s-triazine, N,
Active halogen compounds such as N'-bis(2-chloroethylcarbamyl)piperazine; bis(2,
3-epoxypropyl) methylpropylammonium p-toluenesulfonate, 1,4-bis(2',3'-epoxypropyloxy)butane, 1,
3,5-triglycidyl isocyanurate, 1,
3-diglycidyl-5-(γ-acetoxy-β-
Epoxy compounds such as (oxypropyl) isocyanurate; 2,4,6-triethyleneimino-
s-triazine, 1,6-hexamethylene-N,
Ethyleneimine compounds such as N'-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-di(methanesulfonoxy)ethane, 1,4-di(methanesulfonoxy)butane, 1,5- Examples include methanesulfonic acid ester compounds such as di(methanesulfoneoxy)pentane; furthermore, carbodiide compounds; isoxazole compounds; and inorganic compounds such as chromium alum. Among these hardening agents, compounds having active vinyl groups and/or inorganic compounds can be particularly preferably used. In addition to the nonionic surfactant and anionic surfactant according to the present invention, the photographic material of the present invention includes:
Other known surfactants can be used in combination. Examples of other surfactants that can be used in combination include higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, and cationic surfactants such as phosphonium or sulfonium;
Examples include anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, and phosphoric esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric or phosphoric esters of amino alcohols. be able to. Further, a fluorine-containing surfactant can also be used in combination. In addition, the photographic light-sensitive material of the present invention has a photographic constituent layer containing U.S. Pat.
The alkyl acrylate latex described in No. 5331 and the like can be included. The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape. Irregulars may have crystalline forms, or may have a composite form of these crystalline forms. It may also consist of a mixture of particles of different crystalline forms. These photographic emulsions are Chimie ef by P. Glafkides
Physique Photographique (published by Paul Monhel)
1967), Photographic Emulsion by GFDuffin
Chemistry (The Focal Press, 1966), VL
Making and Coating by Zelikman et al
Photographic Emulsion (published by The Focal Press)
(1964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . Although the silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, Glafkides or
Zelikman et al.'s book or H. Frieser's Die
Grundlagen der Photographischen Prozesse
mit Siberhalogeniden
Akademische
Verlagsgesellschaft, 1968) can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
Described in Nos. 2278947, 2728668, and 3656955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include US Pat.
Described in Nos. 2518698, 2983609, 2983610, and 2694637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in the periodic table group such as platinum, iridium, and palladium can be used.
It is described in issues such as No. 618061. The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. The dyes used include
Included are 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, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto. (Example) Example 1 (1) Preparation of sample: A silver halide emulsion layer with the following composition was coated on an undercoated polyethylene terephthalate film support with a thickness of 180 μm, and on top of that a silver halide emulsion layer with the following composition was applied. A protective layer was applied and dried to prepare a black and white silver halide photosensitive material. The nonionic surfactant and anionic surfactant of the present invention or a comparative surfactant were added to the protective layer. (Emulsion layer) Thickness: Approximately 5μ Composition and coating amount Gelatin 2.5g/m ² Silver iodobromide (silver iodide 1.5 mol%) 5g/m ² 1-phenyl-5-mercaptotetrazole
25mg/m ² (protective layer) Thickness: approx. 1μ Composition and coating amount Gelatin 1.7g/m ² 2,6-dichloro-6-hydroxy-1,
3,5-triazine sodium salt 10 mg/m ² Nonionic surfactant 60 mg/m ² Anionic surfactant of the present invention or anionic surfactant for comparison 25-40 mg/m ² (2) Method for determining antistatic ability: Electrostatic The prevention ability was determined by measuring surface resistivity and static mark occurrence. Surface resistivity is measured by placing a test piece of the sample between 10 cm long brass electrodes with an electrode spacing of 0.14 cm (the part in contact with the test piece is made of stainless steel), and measuring the value for 1 minute using a Takeda Riken insulation meter TR8651. . In the static mark generation test, a late-exposed photosensitive material was placed on a rubber sheet with the surface containing the antistatic material facing downward, and then pressed from above with a rubber roller.
A method was used in which static marks were generated by peeling. Each measurement condition is surface resistivity: 25℃, 25%RH
The static mark generation test was performed at 25℃,
Perform at 25% RH. The humidity of the sample test piece was maintained under the above conditions all day and night. To evaluate the degree of static mark generation, each sample was incubated at 20°C using a developer with the following composition.
It was developed for 5 minutes. Developer composition N-methyl-p-aminophenol sulfate
4g Anhydrous sodium sulfite 60g Hydroquinone 10g Soda carbonate (monohydrate) 53g Potassium bromide 25g Add water to make 1. The evaluation of static marks was based on the following five-level criteria. A: No static marks were observed. B: Some static marks occur. C: Significant static marks occur. D: Significant static marks occur. E: Static marks appear on the entire surface. (3) Photographic property testing method: The sample was tested using a Fujifilm filter SP-
After exposing to tungsten lamp light through 14, it was developed with a developer having the following composition (35℃, 30 seconds).
The photographic properties were examined after fixing and washing. Developer composition Warm water 800ml Sodium tetrapolyphosphate 2.0g Anhydrous sodium sulfite 50g Hydroquinone 10g Sodium carbonate (monohydrate) 40g 1-phenyl-3-pyrazolidone 0.3g Potassium bromide 2.0g Add water and mix to 1000ml (4) Roller Measurement of degree of contamination The sample coated with the emulsion layer and surface protection layer was
Cut into cm x 17.1cm squares. After uniform exposure so that the optical density after processing is 1.0, an automatic processing machine (equipped with a silicone roller conveyor)
(Developer=Fuji Photo Film RD-35℃, fixing bath=Fuji Photo Film Fuji-F35℃, washing bath)
50 sheets were continuously developed using a bath consisting of a bath. After thoroughly drying the water-washed squeeze roller,
The appearance of streak-like density unevenness at the tip of the 51st sample was also investigated. The degree of roller contamination was evaluated according to the following four-level criteria. A: No density unevenness was observed. B: Slight density unevenness occurs. C: Considerable density unevenness occurs. D: Significant density unevenness occurs. The test results of (2) to (4) above are based on the nonionic surfactant represented by the general formula [-1] of the present invention, the anionic surfactant represented by the general formula [], and the comparative compounds (a), ( b) is shown in Table 1. As is clear from Table 1, the photographic material containing the nonionic surfactant and anionic surfactant according to the present invention satisfies all of the static marks, photographic sensitivity, and roller stains.

[Table] Example 2 Same as Example 1, nonionic surfactant represented by general formula [-2] of the present invention, anionic surfactant represented by general formula [], and comparative compound
The evaluation was performed using (a) and (b). The results are shown in Table 2. As shown in Table 2, it is clear that the photographic material containing the nonionic surfactant and anionic surfactant of the present invention has good static marks and photographic sensitivity, and has significantly improved roller staining.

【table】

[Table] Preferred embodiments of the present invention are as follows. 1. A photographic light-sensitive material according to the claims, characterized in that the nonionic surfactant is represented by the general formula [-1] or [-2] described herein. 2 The nonionic surfactant has the general formula described in the text [
-2] A photographic light-sensitive material as claimed in the claims. 3. A photographic light-sensitive material according to claims, characterized in that the anionic surfactant is represented by the general formula [ ] described in the text. 4. A photographic material as claimed in the claims, characterized in that the nonionic surfactant is represented by the general formula [-1] or [-2], and the anionic surfactant is represented by the general formula []. 5. A photographic light-sensitive material according to the claims, characterized in that the nonionic surfactant is represented by the general formula [-2], and the nonionic surfactant is represented by the general formula [].

Claims (1)

[Scope of Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
In the silver halide emulsion layer or other hydrophilic colloid layer, at least one type of the following general formula [-1]
or a silver halide photographic light-sensitive material characterized by containing a nonionic surfactant represented by [-2] and at least one anionic surfactant having a polyoxyethylene group represented by the following general formula []. In the formula, R ₂ , R ₃ , R ₇ , and R ₉ are hydrogen atoms, alkyl groups, aryl groups, alkoxy groups, halogen atoms,
It represents an acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group. In the formula, R ₆ and R ₈ are an alkyl group, an aryl group,
It represents an alkoxy group, a halogen group, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. In the general formula [-2], the substituents on the phenyl ring may be asymmetrical. R ₁ , R ₄ and R ₅ represent a hydrogen atom, an alkyl group, or an aryl group. R ₁ and R ₅ , R ₄ and R ₅ , R ₆ and
R ₇ and R ₈ and R ₉ may be linked to each other to form a ring. (However, R ₁ and R ₅ do not become hydrogen atoms at the same time.) n ₁ , n ₂ , and n ₃ are average degrees of polymerization of ethylene oxide, and are numbers from 2 to 50. Moreover, m is an average degree of polymerization, and is a number from 2 to 50. General formula [] R ₀ -A (-CH ₂ CH ₂ O) - _o4 BD [] In the formula, R ₀ is an alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms, and A is -O- group , -S-
group, -COO- group, [Formula] [Formula] [Formula] (where R ₁₀ represents a hydrogen atom or an alkyl group). B represents an alkyl group, alkenyl group or aryl group, and D represents an anion group. Further, _n4 is the average degree of polymerization of ethylene oxide, and represents a number from 1 to 50.