JPH0119137B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photographic light-sensitive material with improved antistatic properties, and more particularly to a photographic light-sensitive material with improved aging deterioration of the antistatic properties. Photographic materials generally consist of an electrically insulating support and a photographic layer, so during the manufacturing process of the photographic material and during use, it is subject to contact friction or peeling with surfaces of the same or different materials. 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 due to electrostatic charges accumulated before processing being discharged, resulting in dot-like spots or dendritic or feather-like line spots when the photographic film is developed. It is something that happens. These are so-called static marks, and they significantly reduce the commercial value of the photographic film, and in some cases, completely destroy it. For example, if it appears in medical or industrial X-ray film, it can be easily recognized that it will lead to a very dangerous judgment. This problem becomes apparent only after the image is developed, 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 finished products, the separation of the base surface and emulsion surface when winding and switching photographic film is performed, or mechanical parts in automatic X-ray film cameras or fluorescent intensifying screens. This occurs due to contact separation between the 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, static marks are 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 photography, and high-speed automatic processing. There is. The best way to eliminate these static electricity hazards is to increase the electrical conductivity of the material so that the static charge can be quickly dissipated before the stored charge can be discharged. Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. I've been exposed to it.
For example, US Patent No. 2882157, US Patent No. 2972535, US Patent No.
No. 3062785, No. 3262807, No. 3514291, No.
Polymers such as those described in US Pat. No. 3,615,531, US Pat.
No. 2982651, No. 3428456, No. 3457076, No.
Surfactants such as those described in US Pat. No. 3,454,625, US Pat.
Zinc oxide, semiconductors, colloidal silica, etc. as described in No. 3062700, No. 3245833, and No. 3525621 are known. However, many of these materials exhibit specificity depending on the type of film support and photographic composition, and while they may produce good results for certain film supports, photographic emulsions, and other photographic components, others Film supports and photographic components of different colors are not only completely useless in preventing static electricity, but may also have an adverse effect on photographic properties. In particular, it is very difficult to prevent static electricity on a hydrophilic colloid layer, and the surface resistance may not be sufficiently reduced at low humidity.
Adhesion failures often occur between photographic materials or other substances at high temperatures and high humidity. On the other hand, although it has an extremely excellent antistatic effect, it is often unusable because it adversely affects photographic properties such as sensitivity, fog, graininess, and sharpness of photographic emulsions. For example, polyethylene oxide compounds are generally known to have an antistatic effect, but they often have adverse effects on photographic properties such as increased fog, desensitization, and deterioration of graininess. In particular, it is difficult to establish a technology that effectively imparts antistatic properties without adversely affecting the photographic properties of photosensitive materials in which photographic emulsions are coated on both sides of the support, such as direct X-ray photosensitive materials for medical use. It was difficult. Further, even if antistatic properties are carried out, the antistatic property often changes over time, making it particularly difficult to establish a stable antistatic technology. Furthermore, even a compound effective as an antistatic agent may inhibit coating properties when coating a photographic constituent layer. As described above, it is very difficult to apply antistatic agents to photographic materials, and the range of their use is often limited. A first object of the present invention is to provide a photographic material that is antistatic without deteriorating its photographic properties. A second object of the present invention is to provide a photographic material whose antistatic properties change little over time. Another object of the present invention is to improve the coating properties of various photographic coating solutions and form a uniform coating film. These objects of the present invention have been achieved by a photographic material containing a compound represented by the following general formula () in at least one of its photographic constituent layers. General formula () Here, either R ₁ or R ₂ represents a substituted or unsubstituted alkyl group or aryl group, and the other represents a fluorine-substituted alkyl group. When R ₁ or R ₂ represents an alkyl group, the alkyl group preferably has 1 to 30 carbon atoms, particularly 2 to 20 carbon atoms. Examples of substituents for the alkyl group include an alkoxy group, a halogen atom (eg, chlorine, fluorine), an aryl group, an acyloxy group, an aryloxy group, and the like. When R ₁ or R ₂ represents an aryl group, a phenyl group or a naphthyl group is preferred. Examples of substituents for the aryl group include alkyl groups, alkoxy groups, and halogen atoms (eg, chlorine and fluorine). R ₁ or R ₂ represents a fluorine-substituted alkyl group, and as a fluorine-substituted alkyl group,
(CH ₂ )nCmF _2n+1 or (CH ₂ )n(CF ₂ )mH
(however, n=0, 1 or ₂ , m=1 to 12), ( _CH2CH2O ) _n1 ( _CH2 )nCmF2n ₊₁ (however, _n1 =
1 to 4), (CH ₂ CH ₂ O) n ₁ (CH ₂ ) n (CF ₂ ) mH,
(CH ₂ ) n ₁ NHCO (CF ₂ ) mH or (CH ₂ )
n ₁ NHCOCmF _2n+1 can be mentioned. M represents a cation, such as a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, ammonium,
Examples include amines. Particularly preferable examples include Na ⁺ , K ⁺ , Ca ⁺⁺ , NH ₄ ⁺ , C ₂ H ₅ -
Examples include N+H ₃ , HN+(C ₂ H ₅ ) ₃ , H ₃ N+CH ₂ CH ₂ OH, and the like. Specific examples of the compound represented by the general formula () are shown below, but the present invention is not limited thereto. Compound example Synthesis Example 1 (Compound Example-11) 130.1 g of itaconic acid, 150.4 g of decyl alcohol, and 1.5 g of p-toluenesulfonic acid were added to 200 ml of toluene.
The mixture was heated to reflux, and 19.1 ml of water was removed in 8 hours. After the reaction was cooled, the precipitated crystals were collected by filtration and thoroughly washed with water and hexane to obtain monodecyl itaconate in a yield of 128.8 g (50.2%). (mp68.5
~69.5°C) 108.1 g of the above monoester was reacted with 83.3 g of phosphorus pentachloride at room temperature for 1 hour, and the by-produced phosphorus pentachloride was distilled off under reduced pressure to obtain 124 g of residual oil. Next, 60.1 g of the ester-acid chloride obtained above was added dropwise to 75.7 g of dodecafluoroheptanol, 18 g of pyridine, and 10 ml of chloroform at a temperature below 30°C. Then, heat under reflux for 4.5 hours, and after cooling, water,
Washed with dilute sodium bicarbonate water. After distilling off the chloroform, distill it under reduced pressure to obtain a boiling point of 185-195℃/2mm.
78.3g (64.4%) of Hg fraction was obtained. 60.1g of this ester and sodium bisulfite
14.2g was heated under reflux in 14.2g of water (15 hours) After the reaction was completed, water was distilled off. The residue was dissolved in 300 ml of ethanol, and insoluble matter (inorganic matter) was removed to obtain the target compound (10). The yield was 65.8g. Example 2 (Compound Example-12) 65.1 g of itaconic acid, 365.3 g of dodecafluoroheptanol, 1 g of p-toluenesulfonic acid and 100 ml of toluene were heated to reflux, and 12 ml of water was distilled off over 24 hours. Cool the reaction solution, take the precipitated crystals, and add water,
Washed with hexane. Yield: 106 g 88.8 g of monoester was reacted with 41.7 g of phosphorus pentachloride at room temperature, and after further reaction at 55° C. for 2 hours, the by-produced phosphorus oxychloride was distilled off under reduced pressure. yield
92.5g of oil was obtained. Next, 26.0g of 2-ethylhexanol, pyridine
The acid chloride obtained above was added dropwise to a 100 ml solution of chloroform containing 15.8 g at 40°C or lower. After completing the reaction by further heating under reflux for 3 hours, water, diluted sodium bicarbonate solution,
It was washed with water and chloroform was distilled off. Distill the residual oil under reduced pressure to obtain an oil content of bp152-160℃/2mmHg.
Got 69g. Add 64.0g of the above ester to sodium bisulfite.
After heating under reflux (13 hours) with 13.2 g and 20 ml of water, water was distilled off. The residual wax was dissolved in 200 ml of benzene, and after filtering off the insoluble matter, 64.0 g of the target product (12) was obtained. Synthesis Example 3 (Compound Example-9) 35.5 g of itaconic acid, 230 g of dodecafluoroheptanol, 2 g of p-toluenesulfonic acid, toluene
The mixture was heated to reflux at 100 ml, and 4.5 ml of water was distilled off after 20 hours. It was washed with water, diluted caustic soda water, and water, and after distilling off toluene, it was distilled under reduced pressure. bp165-172℃/1.5
The yield was 105g at mmHg. 105g of the above ester and 15g of sodium bisulfite
After heating in 20 ml of water, a homogeneous water-soluble solution was obtained after 9 hours. After the reaction, the water was distilled off, the product was dissolved in ethanol, the insoluble matter was distilled off, and the ethanol was distilled off to obtain a colorless wax. Yield 120g. Synthesis Example 4 (Compound Example-13) Itaconic acid 260.2g, 2-ethylhexanol
247.4g, p-toluenesulfonic acid 3g and toluene
Using 300 ml, the mixture was heated under reflux for 8.5 hours, and 38.4 ml of water was dehydrated. After cooling, insoluble matter was filtered out, the filtrate was washed with water, and toluene was filtered out. The residual oil was distilled under reduced pressure to obtain 314 g (68.2%) of oil (monoester) at bp 158-162°C/2 mmHg. 266.5 g of the above monoester was reacted with 229.1 g of phosphorus pentachloride (at room temperature), and the by-produced phosphorus oxychloride was distilled off under reduced pressure. The oil obtained is a monoester monocarboxylic acid chloride. Next, 57.1 g of the above acid chloride was added dropwise to a solution consisting of 58.1 g of nonafluorohexanol, 22.3 g of triethylamine, and 100 ml of chloroform at a temperature below 5°C, followed by reaction at room temperature for 1 hour and at 70°C for 1 hour. After cooling, the mixture was washed with water, diluted caustic soda water, and water, and chloroform was distilled off, followed by vacuum distillation.
bp148-154℃/1-2mmHg. The yield was 27.1g. Subsequently, 24.3 g of the above ester, 5.5 g of sodium bisulfite, and 10 ml of water were added and reacted at 100°C for 7 hours. After cooling, 10 ml of ethanol was added and the mixture was washed three times with 50 ml of hexane. After distilling off the ethanol and water, dissolve in 50 ml of ethanol and filter out the insoluble matter.
The target compound (13) was obtained by drying the filtrate under reduced pressure.
Obtained 13.3g. The compound of the present invention is added to at least one of the photographic constituent layers of a photographic light-sensitive material, such as a silver halide emulsion layer, a surface protective layer, an intermediate layer, a back layer, an overcoat layer, etc., but especially a surface protective layer, a back coat layer, etc. It is preferable to add it to a surface layer such as a layer or an overcoat layer. When applying the compound of the present invention to a photographic light-sensitive material, it is dissolved in water, an organic solvent such as methanol, isopropanol, acetone, or a mixed solvent thereof, and then added to a coating solution for a surface protective layer, a back layer, etc. Apply by dip coating, air knife coating, or extrusion coating using a hopper as described in U.S. Pat. No. 2,681,294 or U.S. Pat.
Two or more layers may be applied simultaneously by methods such as those described in No. 3,526,528, or by immersion in an antistatic liquid. Further, if necessary, an antistatic liquid containing the compound of the present invention is further coated on the protective layer. The amount of the compound represented by the general formula () used in the present invention is 0.05 to 50 mg/ ^m2 , particularly preferably 1 to 20 mg/ ^m2 . Of course, the above range varies depending on the type of photographic film base used, the photographic composition, the form, and the coating method. Examples of the support used in the photographic material of the present invention include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film,
There are polycarbonate films and other laminates of these materials. More specifically, baryta or α-olefin polymers, particularly polyethylene, polypropylene, ethylene-butene copolymers, etc. with 2 carbon atoms
Examples include paper coated or laminated with a polymer of ~10 α-olefins. In the photographic material of the present invention, each photographic constituent layer may also contain the following binder.
Examples of hydrophilic colloids include proteins such as gelatin, colloidal albumin, and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N-
Examples include vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives and partial hydrolysates thereof. Mixtures of two or more of these colloids are used if necessary. Among these, gelatin is the most used, and gelatin here refers to so-called lime-treated gelatin, acid-treated gelatin, and oxygen-treated gelatin. The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and an aqueous halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. Silver halide grains are treated with chemical sensitizers (e.g., sodium thiosulfate, N,N,N'-trimethylthiourea, monovalent gold thiocyanate complex, monovalent gold thiosulfate complex, stannous chloride, hexamethylenetetramine, etc.). ), it is possible to increase the sensitivity without coarsening the particles. Photographic emulsions may be spectral sensitized or supersensitized as necessary by using polymethine sensitizing dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. Can be done. Furthermore, various compounds can be added to the photographic emulsion of the photographic light-sensitive material used in the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material. These compounds are 4-hydroxy-6-methyl-1,3,3a,
A large number of compounds have been known for a long time, including 7-tetrazaindene-3-methyl-benzothiazole and 1-phenyl-5-mercaptotetrazole, as well as many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. . Examples of compounds that can be used include TH James and CEK Mees,
"The Theory of the Photographic Process"
The original document is listed in the 3rd edition (1966), published by MacMillan. The photographic coupler that can be applied to the photographic light-sensitive material of the present invention develops color through oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative or an aminophenol derivative) during a color development process. It includes compounds that can. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides). , etc., and cyan couplers include naphthol couplers, phenol couplers, etc. The photosensitive material of the present invention contains hydroquinone derivatives, aminophenol derivatives,
It may also contain gallic acid derivatives, ascorbic acid derivatives, etc. Further, the compound represented by the general formula of the present invention can be used in combination with a higher alcohol. Examples of higher alcohols include amyl alcohol, cyclohexanol, octanol, cetyl alcohol, and stearyl alcohol. The photographic light-sensitive material of the present invention contains hydroquinone derivatives, gallic acid derivatives, p
-Alkoxyphenols, P-oxyphenol derivatives, bisphenols, etc. can be used. Compounds known as gelatin hardeners can be used in the photographic material of the present invention. Typical examples include mucochloric acid, formaldehyde, trimethylolmelamine, glyoxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4
-Aldehyde compounds such as dioxane, succinic aldehyde, and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 1,3,5-
Triacryloyl-hexahydro-s-triazine, 1,3,5-trivinylsulfonyl-hexahydro-s-triazine, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(α
-Activated vinyl compounds such as (vinylsulfonylacetamido)ethane; 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,
Active halogen compounds such as 4-dichloro-6-methoxy-s-triazine; ethyleneimine compounds such as 2,4,6-triethyleneimino-s-triazine; and the like. A surfactant may be added alone or in combination to the photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, sensitization and other photographic property improvements, and charge sequence adjustment. These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, phosphonium or Cationic surfactants such as sulfoniums; anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, and phosphoric esters;
Ampholytic surfactants include amino acids, aminosulfonic acids, and sulfuric or phosphoric acid esters of amino alcohols. In addition, in the present invention, lubricating compositions such as U.S. Pat. No. 3,079,837, U.S. Pat.
No. 3545970, No. 3294537 and Japanese Published Patent No. 1972
- Modified silicone as shown in No. 129520 can be included in the photographic constituent layer. The photographic light-sensitive material of the present invention contains the polymer latex described in U.S. Pat. No. 3,411,911, U.S. Pat. Polymethyl methacrylate and the like can be included. By implementing the present invention, failures caused by statics that occur during the manufacturing process and/or during use of photographic light-sensitive materials have been improved. For example, in the practice of the present invention, contact between the emulsion side and the back side of a photographic material, contact between emulsion side and emulsion side, and contact between the emulsion side and the back side of a photographic light-sensitive material and materials with which photographic light-sensitive materials commonly come into contact, such as rubbers, metals, plastics, and fluorescent enhancers, can be removed. The occurrence of static marks caused by contact with photosensitive paper etc. was significantly reduced. Particularly surprising, as shown in the Examples below, is that when the compound used in the present invention is applied to the outermost layer of a photographic light-sensitive material, the amount of charge is significantly reduced, and these properties hardly change over time. It is. Next, the effects of the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Example 1 Samples (1) to (12) each consisting of a protective layer, an emulsion layer, a polyethylene terephthalate ester support, an emulsion layer, and a protective layer were coated and dried according to a conventional method. The composition of each layer is shown below. (Emulsion layer) Binder: Gelatin 2, 5g/m ² Coated silver amount: 5g/m ² Halogenated composition: AgI 1.5 mol% + AgBr 98.5 mol% Hardener: Chromium alum 0.8 g/100 g Binder Fogging inhibitor : 1-phenyl-5-mercaptotetrazole 0.5g/Ag100g (protective layer) Binder: Gelatin 1.7g/m ² + Potassium polystyrene sulfonate (average molecular weight approximately 70,000) 0.3g/
^m2 hardener: 2-hydroxy-4,6-dichloro-
s-triazine sodium salt 0.4g/100g binder Antistatic agent: See Table 1 for types and amounts used.As shown in Table 1, for comparison with the compounds of the present invention, saponins and those described in JP-A-51-32322 are used. A fluorinated sulfosuccinic acid compound was added to the protective layer as shown in the photo film, which was coated and dried. After conditioning the film at 25°C and 25% RH for 2 hours, the amount of static marks generated was determined by the following method. was measured. Measuring the amount of static marks generated: Lay the surface of the photographic film sample on a white rubber plate, press the white rubber plate with a rubber roller to apply a certain amount of friction, remove the white rubber plate, develop, fix, and wash with water. The amount of static marks generated was investigated. The results are shown in Table 1.

[Table] ｜
CH ₂ −COOCH ₂ CH(C ₂ H ₅ )C ₄ H ₉
The evaluation of the amount of static marks generated was as follows: A: No static marks were observed at all. B: Some static marks were generated. C: Quite a bit; D: Significantly; E: Completely. Table 1 shows that when the fluorinated sulfoitaconic acid surfactant of the present invention is added to the protective layer, the antistatic properties are improved, static marks do not occur, and the antistatic properties have good aging properties. I understand. Example 2 Samples (1), (2), which were composed of a cellulose triacetate support, an antihalation layer, a red photosensitive layer, an intermediate layer, a green photosensitive layer, a yellow filter layer, a blue photosensitive layer, and a protective layer. Apply (3) and (4) according to the usual method,
I made it by drying it. The composition of each layer is shown below. (Anti-halation layer) Binder: Gelatin 4.4g/m ² Hardener: 1,3-bis(vinylsulfonyl)
Propanol-2 1.2g/100g Binder Coating aid: Sodium dodecylbenzenesulfonate 4mg/m ² Antihalation ingredient: Black colloidal silver 0.4g/
m ² (red photosensitive layer) Binder: Gelatin 7g/m ² Hardener: 1,3-bis(vinylsulfonyl)
Propanol-2 1.2g/100g Binder Coating aid: Sodium dodecylbenzenesulfonate 10mg/m ² Coating silver amount: 3.1g/m ² Silver halide composition: 2 mol% AgI + 98 mol% AgBr Fog inhibitor: 4-hydroxy-6 -Methyl-
1,3,3a,7-tetrazaindene 0.9g/
Ag100g Color former: 1-hydroxy-4-(2-acetylphenyl)azo-N-[4-(2,4-di-tert
-amylphenoxy)butyl]-2-naphthamide 38g/Ag100g Sensitizing dye: anhydro-5,5'-dichloro-9
-Ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide pyridinium salt
0.3g/Ag100g (intermediate layer) Binder: Gelatin 2.6g/ ^m2 Hardener: 1,3-bis(vinylsulfonyl)-
Propanol-2 1.2g/100g Binder Coating aid: Sodium dodecylbenzenesulfonate 12mg/m ² (green photosensitive layer) Binder: Gelatin 6.4g/m ² Hardener: 1,3-bis(vinylsulfonyl)
Propanol 2 1.2g/100g Binder Coating aid: Sodium dodecylbenzenesulfonate 9mg/m ² Coating silver amount: 2.2g/m ² Silver halide composition: AgI 3.3 mol% + AgBr 96.7
Mol% Stabilizer: 4-hydroxy-6-methyl-1,
3,3a,7 tetrazaindene 0.6g/Ag100g Color former: 1-(2,4,6-trichlorophenyl)-3-{3-[(2,4-di-tert-amylphenoxy)acetamide}-4 -(4-methoxyphenyl)azo-5-pyrazolone 37g/Ag100g Sensitizing dye: anhydro-5,5'-diphenyl-
9-Ethyl-3,3'-di(2-sulfoethyl)oxacarbocyanine hydroxide pyridinium salt 0.3g/Ag100g (yellow filter layer) Binder: Gelatin 2.3g/m ² Filter component: Yellow colloidal silver 0.7g/m ² Hardener: 1,3-bis(vinylsulfonyl)-
Propanol 2 1.2g/100g Binder Surfactant: 2-sulfonatosuccinic acid bis(2
-Ethylhexyl) ester sodium salt 7
mg/m ² (blue photosensitive layer) Binder: Gelatin 7g/m ² Hardener: 1,3-bis(vinylsulfonyl)
Propanol 2 1.2g/100g Binder Coating aid: Sodium dodecylbenzenesulfonate 8mg/m ² Coating silver amount: 2.2g/m ² Silver halide composition: AgI 3.3 mol% + AgBr 96.7
Mol% Stabilizer: 4-hydroxy-6-methyl-1,
3,3a,7 tetrazaindene 0.4g/Ag100g Color former: 2'-chloro-5'-[2-(2,4-di-tert-amylphenoxy)butyramide]-α
-(5,5'-dimethyl-2,4-dioxo-3-
oxazolidinyl)-α-(4-methoxybenzoyl)acetanilide 45g/Ag100g (protective layer) Binder: gelatin 2g/m ² + styrene-maleic anhydride (1:1) copolymer with an average molecular weight of approximately 100,000 0.3g/ ^m2 Hardener: 1,3-bis(vinylsulfonyl)-
Propanol 2 1.2g/100g binder Coating aid: Sodium dioctyl sulfosuccinate 5mg/m ² Sample (11) consists only of the above composition, and sample (12) has the same composition as sample (11) plus a protective layer. Examples of compounds of the invention
(2) at 5 mg/m ² , sample (13), Example 1 sample (7) and
Contains 5 mg/m ² of the comparative compound used in (8). The results of measuring the antistatic properties of samples (11), (12), and (13) are shown in Table 2.

[Table] From the results in Table 2, it can be seen that when the fluorinated sulfoitaconic acid surfactant of the present invention is added to the protective layer, the antistatic properties are significantly improved. Moreover, it does not deteriorate over time. Example 3 Primed polyethylene terephthalate film base with 6% gelatin and silver iodobromide (silver iodide)
A photographic emulsion coating solution is prepared by adding additives such as stabilizers and hardeners to a high-sensitivity emulsion for X-ray photography containing 6% (1.5 mol%), and an aqueous solution mainly consisting of gelatin, which does not contain an antistatic agent, is used as a surface protective layer. Continuously applied and dried. (The composition of each layer is shown in Table 3). This sample obtained was divided into 3% each of the compounds shown in Table 4.
They were immersed separately in an aqueous solution for 30 seconds. For comparison, saponin and the comparative compound used in Example 1 were treated in the same manner. These photographic film samples are 25
After adjusting the humidity for 2 hours at ℃ and 25% RH, the surface of the sample and a white rubber plate were placed on top of each other, and the white rubber plate was pressed with a rubber roller at 25℃ and 40% RH to give a constant friction. After that, the white rubber plate was removed, developed and fixed with a developer having the composition shown below, and the amount of static marks produced was examined. These results are shown in Table 4. Developer composition Warm water (50℃) 700ml N-methyl-p-aminophenol sulfate 4g Anhydrous sodium sulfite 60g Hydroquinone 10g Sodium carbonate (monohydrate) 53g Potassium bromine 25g Add water

【table】

[Table] As can be seen from Table 4, the photographic film treated with the aqueous solution of the fluorinated itaconic acid surfactant of the present invention was
It can be seen that no static marks were observed and the antistatic properties hardly deteriorated even after 3 months. In the case of other fluorinated sulfosuccinic acid surfactants such as those described in JP-A-51-32322, the initial performance is slightly inferior to that of the compound of the present invention, but after 3 months, it shows antistatic properties. The condition worsened, and the static marks were severe.

Claims (1)

[Scope of Claims] 1. A photographic light-sensitive material characterized in that at least one of the constituent layers of the photographic light-sensitive material contains a compound represented by the following general formula. (general formula) In the general formula, either R ₁ or R ₂ is
One represents a substituted or unsubstituted alkyl group or aryl group, and the other represents a fluorine-substituted alkyl group. M represents a cation.