JPH0377976B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photographic light-sensitive material, and particularly to a photographic light-sensitive material with improved antistatic properties. (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 is exposed to light due to the discharge of electrostatic charges accumulated before processing, resulting in dots or dendritic or feather-like streaks 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 peeling between the support surface and the emulsion surface, etc. Or, it may occur due to contact peeling between the X-ray film and a mechanical part in an automatic photographing machine or a fluorescent intensifying screen. 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. Especially 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. There is. 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. Antistatic agents are required to be used in photographic materials, such as not causing the photographic materials to become easily pocked), not accelerating the fatigue of processing solutions for photographic materials, and not reducing the adhesive strength between the constituent layers of photographic materials. application is subject to numerous constraints. One way to eliminate the problems caused by static electricity is to increase the electrical conductivity of the surface of the photosensitive material so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged. Therefore, methods of improving the electrical conductivity of supports and various coated surface layers of photographic light-sensitive materials have been considered, and the use of ionic polymers has been attempted as one of these methods. For example, Special Publication No. 57-53587, No. 57
−15375, German Patent No. 1745061, Special Publication No. 1977−
No. 23827, No. 55-14415, No. 55-15267, JP-A-48-89979, U.S. Patent No. 2279410, No.
No. 3791831 and Japanese Patent Publication No. 47-28937 disclose attempts to utilize (anionic) polymers having carboxyl groups for antistatic purposes in photographic light-sensitive materials. However, these polymers are water-soluble, and when a silver halide photographic light-sensitive material to which these polymers are added is processed, these polymers are eluted into the (aqueous) processing solution and are dissolved in the processing solution. Problems such as accumulation and contamination of silver halide photographic light-sensitive materials that are subsequently developed, or leaving minute elution marks on the surface of silver halide photographic light-sensitive materials, causing cloudiness in the silver halide photographic light-sensitive materials. It was hot. In addition, these polymers also have the problem that these polymers diffuse from the layer of the silver halide photographic light-sensitive material to which they are added into other layers, resulting in a significant decrease in antistatic performance. Ta. In order to solve these problems, an attempt to form a crosslinked latex from a polymer of acrylic acid or methacrylic acid is described in US Pat. No. 4,301,240. This crosslinked polymer of acrylic acid or methacrylic acid was able to solve the above-mentioned problems of the non-crosslinked polymer having carboxyl groups. However, although this crosslinked polymer of acrylic acid or methacrylic acid has sufficient antistatic power at normal humidity to high humidity, it does not have sufficient antistatic power at low humidity, and may cause static marks to appear on photographic materials. It was virtually impossible to prevent it. We have conducted intensive research aimed at developing an antistatic agent that takes advantage of the features of crosslinked polymers and has sufficient antistatic power even at low humidity, and as a result, we have achieved the present invention. A major feature of the crosslinked polymer of the present invention is that it has a monomer represented by the general formula () as a copolymer component. General formula () Here, R ₂ , R ₃ , R ₄ and n are as already shown. (Object of the Invention) An object of the present invention is to provide a silver halide photographic material which is sufficiently prevented from charging. A second object of the present invention is to provide a silver halide photographic material which is sufficiently prevented from charging even at particularly low humidity. A third object of the present invention is to provide a silver halide photographic material which is antistatic and does not generate scum during development. A fourth object of the present invention is to provide an antistatic silver halide photographic material that does not become cloudy during development. (Structure of the Invention) These objects are a silver halide photographic light-sensitive material having at least one silver halide emulsion layer, in which at least one layer other than the emulsion layer contains a crosslinked polymer represented by the following general formula (). This was achieved by a silver halide photographic material characterized by containing: General formula () In the formula, R ₁ and R ₂ represent a hydrogen atom, a methyl group or a carboxylmethyl group, R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an acyl group having 1 to 7 carbon atoms, and R _Four
represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₃ and R ₄ may be linked to each other to form a ring. Further, each group of R ₃ and R ₄ is unsubstituted or substituted. L represents a divalent, trivalent or tetravalent linking group. l represents 0 or 1, m represents an integer of 1 to 3, and n represents an integer of 1 to 10. A represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. B represents a monomer unit obtained by copolymerizing a copolymerizable crosslinking monomer having at least two copolymerizable ethylenically unsaturated groups.
M represents a cation. w is 10 to 90 mol%, x
is 3 to 88 mol%, y is 0 to 50 mol%, z is 2 to 30
It is mole%. The crosslinked polymer of the present invention will be explained in detail below. R ₁ and R ₂ each include a hydrogen atom or an unsubstituted alkyl group such as a methyl group, an ethyl group, or an n-propyl group;
Examples include substituted alkyl groups such as carboxymethyl group. Among these, a hydrogen atom, a methyl group, or a carboxymethyl group is preferred. R ₃ is a hydrogen atom, methyl group, ethyl group, n
-propyl group, i-propyl group, n-butyl group,
Unsubstituted alkyl groups such as i-butyl group, n-hexyl group, n-dodecyl group, substituted alkyl groups such as benzyl group, phenethyl group, 2-chloroethyl group, cycloalkyl group such as cyclohexyl group, phenyl group, p- Examples include unsubstituted or substituted aryl groups such as methylphenyl group and p-chlorophenyl group; unsubstituted or substituted acyl groups such as acetyl group, benzoyl group, and p-methoxybenzoyl group; Lower groups are preferred.
R ₄ is a hydrogen atom, methyl group, ethyl group, n-
Examples include unsubstituted or substituted alkyl groups such as a propyl group and a chloromethyl group, and among these, a hydrogen atom or a methyl group is preferred. When R ₃ and R ₄ are linked to each other to form a ring, an example of the ring is a tetrahydrofuran ring. L is a divalent, trivalent or tetravalent linking group, in the case of a divalent linking group -Q-, in the case of a trivalent linking group

[Formula] In the case of a tetravalent linking group teeth

[Formula] is preferred. Here, Q is a divalent linking group, examples of which are alkylene groups (e.g. methylene group, ethylene group, trimethylene group),
arylene group (e.g. phenylene group),

[Formula] (However, X represents an alkylene group or arylene group having 1 to about 6 carbon atoms. The same applies hereinafter) (For example,

【formula】),

[Formula] (for example

【formula】),

【formula】 (for example

【formula】),

[Formula] (for example

【formula】),

[Formula] (for example

【formula】),

[Formula] (for example

【formula】),

[Formula] (for example

[Formula]), etc. can be mentioned. l is 0 or 1. m is an integer of 1 to 3, preferably 1 or 2. n is an integer of 1 to 10, preferably an integer of 1 to 5. Examples of monomer A include ethylene, propylene,
Nobran, isobran, styrene, α-methylstyrene, vinyltoluene, ethylenically unsaturated esters of fatty acids (e.g. vinyl acetate, allyl acetate), esters of ethylenically unsaturated carboxylic acids (e.g. methyl methacrylate, ethyl methacrylate, n-butyl methacrylate) , n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyacrylate, n-hexyl acrylate, 2-ethylhexyl acrylate), monoethylenically unsaturated compounds (e.g. acrylonitrile) or diels (e.g. butadiene, isoprene), etc. be able to. Examples of monomer B include divinylbenzene, trivinylcyclohexane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, Erythritol tetraacrylate is mentioned. Examples of M include monovalent cations such as hydrogen ions, sodium ions, potassium ions, lithium ions, cesium ions, and ammonium ions, as well as polyvalent cations such as calcium ions, barium ions, and aluminum ions. Among these, monovalent cations are preferred. w is 10 to 95 mol%, preferably 30 to 80 mol%,
x is 3 to 88 mol%, preferably 10 to 60 mol%, y
is 0 to 50 mol%, preferably 0 to 30 mol%, and z is 2 to 30 mol%, preferably 5 to 20 mol%. The method for synthesizing the crosslinked polymer of the present invention is shown below.
The present invention is not limited to these. First, the monomers represented by the general formula (), the monomers represented by the general formula (), the monomers represented by A in the general formula (), and the monomers represented by B in the general formula (), for example, are researched. Disclosure (Research
Examples include a method of direct emulsion copolymerization in water, followed by neutralization with an alkali, if necessary, as described in Vol. 16, Section 16102 of Disclosure. General formula () Here, R ₁ , L, l and m are as already shown. General formula () Here, R ₂ , R ₃ , R ₄ and n are as already shown. Second, the monomer represented by the above general formula (), the monomer represented by A in the general formula (), and the monomer represented by B in the general formula () are emulsion copolymerized in water to obtain the general formula ().
An example of this method is to prepare a crosslinked polymer dispersion represented by the following formula and then saponify it with an alkali in the same manner as described in US Pat. No. 4,301,240. General formula () Here R ₂ , R ₃ , R ₄ , n, A, B, w, x, y,
z is as already shown. Furthermore, thirdly, the monomer represented by the general formula (), the monomer represented by the general formula (), the monomer represented by A in the general formula (), and the monomer represented by B in the general formula (), for example, in the US patent An example of this method is to carry out inverse emulsion copolymerization in the same manner as the method described in No. 4301240, then redisperse the produced crosslinked polymer in water, and further neutralize with an alkali if necessary. Among these methods, a preferred method is selected depending on the type of each monomer and the copolymerization ratio. Examples of the crosslinked polymer of the present invention are shown below. Examples of synthesis of the crosslinked polymer dispersion of the present invention are shown below. Synthesis Example 1 Synthesis of Crosslinked Polymer Example 1 In a 2L three-necked flask equipped with a stirrer, reflux condenser, and thermometer, 480ml of distilled water and an emulsifier (Sanyo Chemical Co., Ltd.) were added.
(commercially available under the trade name Sandetto BL) 1.95g and methoxyethyl acrylate
A mixed solution of 104.1 g and 26.0 g of divinylbenzene was added, and the mixture was stirred at 90° C. and 250 rpm under a nitrogen stream. After the air in the vessel was sufficiently replaced with nitrogen, a solution of 0.54 g of potassium persulfate dissolved in 30 ml of distilled water was added to start emulsion polymerization. After heating and stirring at 90℃ for 1.5 hours, the crosslinked polymer dispersion (latex) became cloudy.
I got it. Furthermore, add 0.054g of potassium persulfate to distilled water.
After adding the solution dissolved in 10 ml and continuing heating and stirring for 30 minutes, the mixture was cooled to room temperature. After some aggregates were separated, 629.5 g of a crosslinked polymer dispersion (latex) with a solid content concentration of 19.7 wt% was obtained. The crosslinked polymer particle diameter determined by dynamic light scattering was 0.154μ. The above crosslinked polymer dispersion (latex) was placed in a separate 3L three-necked flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel, and the mixture was heated at 300 rpm at room temperature.
Add 4.19 g of potassium hydroxide to distilled water while stirring.
A solution dissolved in 183 ml was added dropwise over 1 hour. After further stirring at room temperature for 2 hours, the mixture was heated to 98-99°C and stirred for 2 and a half hours. Then potassium hydroxide 7.42
A solution prepared by dissolving 10 g in 183 ml of distilled water was added dropwise over 30 minutes, and the mixture was heated and stirred at 98 to 99°C for 3 and a half hours. Furthermore, a solution of 25.6 g of potassium hydroxide dissolved in 632 ml of distilled water was added dropwise over 30 minutes, and the mixture was heated and stirred at 98 to 99° C. for 12 hours. The mixture was cooled to room temperature, purified by dialysis, and then concentrated to obtain 1237 g of a dispersion of Crosslinked Polymer Example 1. The solid content concentration was 8.77 wt%, the saponification rate determined by acid-base titration was 72.5%, and the crosslinked polymer particle diameter determined by dynamic light scattering was 0.431 μ. Synthesis Example 2 Synthesis of Crosslinked Polymer Example 6 Add 1 liter of distilled water to a 3L three-necked flask equipped with a stirrer, reflux condenser, thermometer, and constant flow rate dropping pump.
, emulsifier (same as the emulsifier used in Synthesis Example 1)
4.45 g was added and stirred at 94-95°C and 250 rpm under a nitrogen stream. After sufficiently replacing the air in the vessel with nitrogen, dissolve (1) a mixed solution of 90.0 g of acrylic acid, 32.5 g of methoxyethyl acrylate, and 58.6 g of pentaerythritol tetraacrylate, and (2) 2.8 g of potassium persulfate in 140 ml of distilled water. (3) A solution in which 1.4 g of sodium bisulfite and 0.56 g of ferrous chloride were dissolved in 140 ml of distilled water were simultaneously added dropwise over an hour and a half. After the dropwise addition was completed, the mixture was heated and stirred for 15 minutes, and then a solution of 2.8 g of potassium persulfate and 2.8 g of sodium bisulfite dissolved in 140 ml of distilled water was added, and the mixture was further heated and stirred for 1 hour and 15 minutes. Next, a solution of 40.0 g of sodium hydroxide dissolved in 200 ml of distilled water was slowly poured into the solution to neutralize it, and then cooled to room temperature. Crosslinked polymer example 6, excluding some aggregates
1751 g of a dispersion of was obtained. Solid content concentration is 11.0wt%,
The particle size of the crosslinked polymer determined by dynamic light scattering was 0.229μ. The amount of the crosslinked polymer represented by the general formula () varies depending on the type, form, coating method, etc. of the photographic material used. However, in general, the amount used is 0.1 per m ² of photographic material.
-10g is good, especially 0.5-5g is desirable. The method for applying the crosslinked polymer represented by the general formula () into the antistatic layer of a photographic light-sensitive material is to use water, an organic solvent (for example, methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, dioxane, dimethylformamide, formamide). , dimethyl sulfoxide, methyl cellosolve, ethyl cellosolve, etc., especially methanol,
(preferably ethanol) or a mixed solvent thereof may be added and dispersed, followed by spraying, coating, or immersion in the solution and drying. Further, it may be used together with a binder such as gelatin, polyvinyl alcohol, cellulose acetate, cellulose acetate phthalate, polyvinyl formal, or polyvinyl butyral to form an antistatic layer. Particularly favorable results can be obtained when a fluorine-containing surfactant and a matting agent are used in combination with the layer containing the crosslinked polymer represented by the general formula () of the present invention. Great for preventing tick marks. Furthermore, the above layer may contain additives for various purposes such as a curing agent, a slip agent, and an antihalation dye. Matting agents that can be used in combination with the crosslinked polymer represented by the general formula () of the present invention to obtain a preferable effect include barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, powdered silica, and titanium oxide. etc. The particle size of the matting agent is preferably 1 to 10 microns, particularly 1 to 5 microns. The amount of matting agent used is preferably 1 to 1000 mg, particularly 10 to 300 mg per m ² of the light-sensitive material. A fluorine-containing surfactant particularly preferably used in combination with the crosslinked polymer of the present invention is represented by the following general formula. General formula () Rf-A-X In the formula, Rf represents a partially fluorinated or fully fluorinated substituted or unsubstituted alkyl group, alkenyl group, or aryl group containing at least 3 fluorine atoms. . A represents a divalent linking group, and X
represents a water-soluble group. A preferably represents an alkyl group, an aryl group, or an alkylaryl group, which is a divalent substituted or unsubstituted linking group interrupted by a heteroatom such as oxygen, an ester group, an amide group, a sulfonyl group, or sulfur. It's okay if it's hot. X is a hydrophilic group, for example, a polyoxyalkylene group of the general formula -(B-O) _o5 R ₁₃ (where B is -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ - or

[Formula] is represented, and n5 represents the average degree of polymerization of the polyoxyalkylene group, and is a number from 1 to 50. ( _R13 represents a substituted or unsubstituted alkyl group or aryl group)
Nonionic group represented by, hydrophilic betaine group, e.g.

[Formula] and

[Formula] (In the formula, AlK is a lower alkylene group having 1 to 5 carbon atoms, such as methylene, ethylene,
propylene, butylene, R ₁₄ and R ₁₅ represent a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group such as a methyl group, an ethyl group, a benzyl group, etc.) and a hydrophilic cation group, such as

[Formula] (wherein R ₁₄ , R ₁₅ , R ₁₆ have the same meanings as R ₁₄ above, and Y represents an anion), and preferably a hydrophilic anion group such as -SO ₃ M, -OSO ₃ M,−COOM,

Examples include [Formula]. M here represents an inorganic or organic cation. Specific examples of typical fluorine-containing surfactants of the present invention are shown below. Compound example-1 C ₇ F ₁₅ COOH -2 H- (CF ₂ -) ₈ CH ₂ COONH ₄ -3 C ₈ F ₁₇ SO ₃ K -5 H- (CF ₂ -) ₆ COOCH ₂ CH ₂ CH ₂ SO ₃ Na −10 C ₈ F ₁₇ CH ₂ CH ₂ O— (CH ₂ CH ₂ O—) _o5 H n5: 12 The amount of the fluorine-containing surfactant used in the present invention is generally 0.001 to 1 g per 1 m ² of the photographic material.
5 to 300 mg is particularly preferred. Examples of the antistatic layer containing the crosslinked polymer of the present invention include an undercoat layer on the same side as the emulsion layer, an intermediate layer, a surface protective layer, an overcoat layer, and a back layer on the opposite side to the emulsion layer. Among these, in particular, a surface protective layer,
An outermost layer such as an overcoat layer or a back layer or a layer adjacent thereto is preferred. Supports to which the crosslinked polymer of the present invention can be applied include:
For example, polyolefins such as polyethylene,
Supports made of films such as polystyrene, cellulose derivatives such as cellulose triacetate, and cellulose esters such as polyethylene terephthalate, or sheets of baryta paper, synthetic paper, or paper coated with these polymer films on both sides, and their similar materials, etc. included. The support used in the present invention may also be provided with an antihalation layer; for this purpose, carbon black or various dyes, such as
Oxole dyes, azo dyes, aryrite dyes,
Examples include styryl dyes, anthraquinone dyes, merocyanine dyes, and tri(or di)allylmethane dyes. As a binder for carbon black dye, cellulose acetate (di or mono),
polyvinyl alcohol, polyvinyl butyral,
polyvinyl acetal, polyvinyl formal,
Polymethacrylic ester, polyacrylic ester, polystyrene, styrene/maleic anhydride copolymer, polyvinyl acetate, vinyl acetate/maleic anhydride copolymer, methyl vinyl ether/maleic anhydride copolymer, polyvinylidene chloride, and Derivatives thereof can be used. The photographic material according to the present invention includes ordinary black-and-white silver halide photographic materials (for example, black-and-white photographic materials, black-and-white photographic materials for X-rays, black-and-white photographic materials for printing,
etc.), ordinary multilayer color photographic materials (e.g.
(color reversal film, color negative film, color positive film, etc.) and various photographic materials. especially,
Great effect on silver halide photographic materials for high-temperature rapid processing and high-sensitivity silver halide photographic materials. Other components that can be used in the photographic material of the present invention, such as the type and manufacturing method of silver halide emulsions, chemical sensitizers, spectral sensitizers, antifoggants, stabilizers, color couplers, binders such as gelatin, There are no particular restrictions on the hardening agent, polymer latex, coating aid, slip agent, antistatic agent other than the antistatic agent of the present invention, and the exposure and development method of the photographic material of the present invention.
Research Disclosure, Vol. 176, pp. 22-31 (1978)
You can refer to the description in December). For example, as the gelatin, acid-treated gelatin or lime-treated gelatin can be preferably used. Polymers include cellulose compounds, agar,
Sugar derivatives such as dextran sodium alginate, starch derivatives, and synthetic hydrophilic colloids (eg, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamide, or derivatives thereof) can be used. As the hardening agent, an active vinyl compound having a vinyl sulfone group or the like or an active halogen compound such as 2,4 dichloro-6-hydroxy-s-triazine is preferably used. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Example 1 (1) Preparation of sample: A silver halide emulsion layer with the following composition was coated on a polyethylene terephthalate film support with a thickness of 180 μm that had been undercoated, and a protective layer with the following composition was further coated on top of the silver halide emulsion layer. The mixture was dried to prepare a black and white silver halide photographic material. (Emulsion layer) Thickness: Approximately 5μ Composition and coating amount Lime-treated 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 Lime-treated gelatin 1.7g/m ² 2,6-dichloro-4-hydroxy-1,
3,5-triazine sodium salt 10 mg/m ² Sodium N-oleyl-N-methyltaurate 7 mg/m ² Sample No. 1 consists only of the above composition, and Sample No. 2 to
In Sample No. 8, in addition to the composition of Sample No. 1, the polymer of the present invention or a comparative polymer was added to the protective layer in an amount equivalent to 1.7 g/m ² . Further, Samples Nos. 9 to 15 were prepared by replacing half of the gelatin in the protective layer of Sample No. 1 with the polymer of the present invention or the comparative polymer (equivalent to 0.85 g/m ² ). (2) Method for determining antistatic property: Antistatic property was determined by measuring surface resistivity and static mark generation. Surface resistivity is measured by placing a test piece of the sample between brass electrodes with an electrode spacing of 0.14 cm and a length of 10 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. . The static mark generation test was conducted by placing an unexposed photosensitive material on a rubber sheet with the antistatic agent-containing surface facing downward, pressing it with a rubber roller from above, and then peeling it off to generate static marks. . Each measurement condition is surface resistivity: 25℃, 25%RH
Measured at 25℃, 10%RH, static mark generation test is 25℃, 25%RH and 25℃, 10%
I went with 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.
Developed for 5 minutes. Developer composition N-methyl-p-aminophenol sulfate
4g Anhydrous 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. The results are shown in Table 1.

[Back layer]

1st layer coating amount (g/m ² ) Binder: Gelatin 1.644 Coating agent: Sulfosuccinic acid dioctyl ester sodium salt 0.585 Thickener: Polystyrene sodium sulfonate 0.023 2nd layer binder: Gelatin 6.00 Coating agent: Sulfosuccinic acid dioctyl ester sodium salt 1.725 Hardener: 2,6-dichloro-4-hydroxy-
1,3,5-triazine sodium salt 0.063 Back protective layer (third layer) Binder: Gelatin 0.612 Matting agent: Polymethyl methacrylate (average particle size 3.5μ) 0.225 Coating agent: Sulfosuccinic acid dioctyl ester sodium salt 1.419 Fluorine-containing interface Activator: Compound Example-4 0.005 Hardener: 2,6-dichloro-4-hydroxy-
1,3,5-triazine sodium salt 0.011 [Color photosensitive layer] 1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer Emulsified dispersion of 2,5-di-t-octylhydroquinone Gelatin layer 3rd layer containing: 1st red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 5 mol %)... Silver coating amount 1.79 g/m ² Sensitizing dye... 6 x per 1 mol of silver 10 ^-5 mol Sensitizing dye... 1.5 x 10 ^-5 mol per mol of silver Coupler A... 0.04 mol per mol of silver Coupler C-1... 0.0015 mol per mol of silver Coupler C- 2...0.0015 mol per mol of silver Coupler D...0.0006 mol per mol of silver 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol%)... Silver Coating amount 1.4 g/m ² Sensitizing dye... 3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye... 1.2 x 10 ^-5 mol per 1 mol of silver Coupler A... Per 1 mol of silver 0.02 mol Coupler C-1...0.0008 mol per mol of silver Coupler C-2...0.0008 mol per mol of silver 5th layer: Intermediate layer 6th layer same as 2nd layer: 1st green sense Emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol%) Coated silver amount 1.5 g/m ² Sensitizing dye... 3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye... 1 silver 1×10 ^-5 mole per mole Coupler B...0.05 mole per mole of silver Coupler M-1...0.008 mole per mole of silver Coupler D...0.0015 mole per mole of silver 7th Layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 5 mol%) Coated silver amount 1.6 g/m ² Sensitizing dye... 2.5 x 10 ^-5 mol increase per 1 mol of silver Sensitive dye... 0.8×10 ^-5 mol per mol of silver Coupler B... 0.02 mol per mol of silver Coupler M-1... 0.003 mol per mol of silver Coupler D... 0.003 mol per mol of silver 0.0003 mol 8th layer: Yellow filter layer Yellow colloidal silver and 2,5-
and an emulsified dispersion of di-t-octylhydroquinone. 9th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 6 mol %)... Coated silver amount 1.5 g/m ² Coupler Y-1... 0.25 mol per 1 mol of silver 10th Layer: 2nd blue-sensitive emulsion layer Silver iodobromide (silver iodide: 6 mol%) Coated silver amount 1.1 g/m ² Coupler Y-1... 0.06 mol per mol of silver 11th layer: Protection Layered polymethyl methacrylate particles (diameter approx.
1.5 μ) Apply a gelatin layer containing sodium dodecylbenzenesulfonate (equivalent to 100 mg/m ² ). In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. Compound sensitizing dye used to prepare the sample: anhydro-5,5'-dichloro-
3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye: anhydro-9-ethyl-3,3'-
Di-(γ-sulfopropyl)-4,5,4'-5'-
Dibenzothiacarbocyanine hydroxide
Triethylamine salt sensitizing dye: anhydro-9-ethyl-5.5'-
Dichloro-3,3'-di-(γ-sulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-
{β-[β-(γ-sulfopropoxy)ethoxy]
Ethylimidazolocarbocyanine hydroxide sodium salt Sample No. 21 consists only of the above composition, and sample No. 22
-27 added 2.13g/ ^m2 of the present invention polymer or comparative polymer to the second layer of the back layer in addition to the composition of sample No.21, and sample Nos.28 to 33 added 2.66g/ ^m2. Created by adding In addition, when the present invention polymer or comparative polymer was added, a considerable amount of gelatin was felt. The antistatic properties were evaluated in the same manner as in Example 1. However, development was carried out using Fuji Film Corporation's CN-16 process. The results are shown in Table 2.

[Table] As is clear from Table 2, the silver halide color photographic light-sensitive material in which Comparative Polymer A was added to the back layer was sufficiently antistatic at 25°C and 25% RH, but at 25°C and 10% RH. It can be seen that static marks occur significantly at low RH humidity. On the other hand, it can be seen that the silver halide photographic material containing the polymer of the present invention added to the back layer has sufficient antistatic properties even at low humidity of 25° C. and 10% RH, and no static marks are observed. 1 A silver halide photograph in which the layer containing the crosslinked polymer represented by the general formula () in the claims is the outermost layer such as a surface protective layer, overcoat layer, back layer, etc. or a layer adjacent thereto. photosensitive material. 2. A silver halide photographic material in which the layer containing the crosslinked polymer represented by the general formula () in the claims is a layer adjacent to a silver halide emulsion layer. 3. A silver halide photographic material in which l in the general formula () is 0 and m is 1 in the claims. 4. A silver halide photographic material as claimed in the claims, wherein the crosslinked polymer has a particle size of 0.05 to 1 μm in water. 5. A method for preventing static electricity in a silver halide photographic material, which comprises containing a crosslinked polymer represented by the general formula () in at least one of the constituent layers of the silver halide photographic material other than the silver halide emulsion layer.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer, which contains a crosslinked polymer represented by the following general formula () in at least one layer other than the emulsion layer. A silver halide photographic material characterized by: General formula () In the formula, R ₁ and R ₂ represent a hydrogen atom, a methyl group or a carboxylmethyl group, R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an acyl group having 1 to 7 carbon atoms, and R _Four
represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₃ and R ₄ may be linked to each other to form a ring. Further, each group of R ₃ and R ₄ is unsubstituted or substituted. L represents a divalent, trivalent or tetravalent linking group. l represents 0 or 1, m represents an integer of 1 to 3, and n represents an integer of 1 to 10. A represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. B represents a monomer unit obtained by copolymerizing a copolymerizable crosslinking monomer having at least two copolymerizable ethylenically unsaturated groups.
M represents a cation. w is 10 to 90 mol%, x
is 3 to 88 mol%, y is 0 to 50 mol%, z is 2 to 30
It is mole%.